Phosphinyl Amidine Compounds, Metal Complexes, Catalyst Systems, and Their Use to Oligomerize or Polymerize Olefins

ABSTRACT

N 2 -phosphinyl amidine compounds, N 2 -phosphinyl amidinates, N 2 -phosphinyl amidine metal salt complexes, N 2 -phosphinyl amidinate metal salt complexes are described. Methods for making N 2 -phosphinyl amidine compounds, N 2 -phosphinyl amidinates, N 2 -phosphinyl amidine metal salt complexes, and N 2 -phosphinyl amidinate metal salt complexes are also disclosed. Catalyst systems utilizing the N 2 -phosphinyl amidine metal salt complexes and N 2 -phosphinyl amidinate metal salt complexes are also disclosed along with the use of the N 2 -phosphinyl amidine compounds, N 2 -phosphinyl amidinates, N 2 -phosphinyl amidine metal salt complexes, and N 2 -phosphinyl amidinate metal salt complexes for the oligomerization and/or polymerization of olefins.

TECHNICAL FIELD OF THE INVENTION

This disclosure relates to N²-phosphinyl amidine compounds and metalcomplexes of N²-phosphinyl amidine compounds and their production. Thedisclosure also relates to methods of producing the N²-phosphinylamidine compounds and the metal complexes of N²-phosphinyl amidinecompounds. The disclosure further relates to catalyst systems utilizingthe N²-phosphinyl amidine compounds, metal complexes of N²-phosphinylamidine compounds, and their use in the oligomerization orpolymerization of olefins.

BACKGROUND OF THE INVENTION

Olefins, also commonly known as alkenes, are important items ofcommerce. Their many applications include employment as intermediates inthe manufacture of detergents, as precursors to more environmentallyfriendly refined oils, as monomers, and as precursors for many othertypes of products. An important subset of olefins are olefin oligomers,and one method of making olefin oligomers is via oligomerization ofethylene, which is a catalytic reaction involving various types ofcatalysts and/or catalyst systems. Examples of catalysts and catalystsystems used commercially in the oligomerization of olefins includealkylaluminum compounds, certain nickel-phosphine complexes, a titaniumhalide with a Lewis acid (e.g., diethyl aluminum chloride), and aselective 1-hexene catalyst system containing a chromium containingcompound (e.g., a chromium carboxylate), a nitrogen containing ligand(e.g., a pyrrole), and a metal alkyl (e.g., alkyl aluminum compounds).

Several non-commercial olefin oligomerization catalyst systems are basedupon metal complexes of pyridine bis-imines, metal complexes ofα-diimine compounds having a metal complexing group, and selectivetrimerization and/or tetramerization catalyst system using a metalcomplex of a compound having a diphosphinylaminyl group. These catalystsystems typically use an alkyl aluminum compound (e.g., aluminoxane) toactivate the metal complexes for olefin oligomerization.

Applications and demand for olefin oligomers (e.g., alpha olefins)continue to multiply, and competition to supply them correspondinglyintensifies. Thus, additional novel and improved catalysts and methodsfor olefin oligomerization are desirable.

SUMMARY OF THE INVENTION

In an aspect, the present invention relates to a compound comprising oneor more N²-phosphinyl amidine groups. In an embodiment, the compound maycomprise only one N²-phosphinyl amidine group. In another embodiment,the compound may comprise only two N²-phosphinyl amidine groups.

In an aspect, the present invention relates to a metal complexcomprising a metal salt complexed to a compound having one or moreN²-phosphinyl amidine groups. In an embodiment, the metal complex maycomprise a Group 4-10 metal salt complexed to a compound comprising oneor more N²-phosphinyl amidine groups. In some embodiments, the metalcomplex may comprise a Group 4-10 metal salt complexed to a compoundcomprises only one N²-phosphinyl amidine group. In other embodiments,the metal complex may comprise a Group 4-10 metal salt complexed to acompound comprises only two N²-phosphinyl amidine groups. In anembodiment, the metal salt may comprise chromium. In an embodiment, themetal salt may be a chromium halide or chromium β-diketonate.

In an aspect, the present invention relates to method of preparing acompound comprising one or more N²-phosphinyl amidine groups. In anembodiment, the method for preparing a compound comprising one or moreN²-phosphinyl amidine groups comprise: a) contacting a metal amide witha nitrile; b) forming a metal amidinate; c) contacting a phosphinehalide with the metal amidinate; and d) forming the compound comprisingthe N²-phosphinyl amidine group. In some embodiments, the method forpreparing an N²-phosphinyl amidine compound may comprise: a) contactingan amine having a —NH₂ group and a compound capable of abstracting aproton from the —NH₂ group; b) forming a metal amide; c) contacting ametal amide and a nitrile; d) forming a metal amidinate; e) contactingthe metal amidinate and a phosphine halide; and f) forming theN²-phosphinyl amidine compound. In other embodiments, the method is amethod for preparing an amidine compound having only one N² hydrogenatom and may comprise: a) contacting a metal amide and a nitrile; b)forming a first metal amidinate; c) contacting the first metal amidinatewith a halogenated compound; d) forming an amidine compound having onlyone N² hydrogen atom; e) isolating the amidine compound having only oneN² hydrogen atom; f) contacting the amidine compound having only one N²hydrogen atom with a compound capable of abstracting a proton from theamidine compound having only one N² hydrogen atom; g) forming a secondmetal amidinate; h) contacting the second metal amidinate and aphosphine halide; and i) forming the N²-phosphinyl amidine compound. Inother embodiments, the method is a method for preparing an amidinecompound having only one N² hydrogen atom and may comprise: a)contacting a first amine and an acid halide; b) forming an amide; c)contacting the amide with phosphorus pentachloride; d) forming anN-substituted α-chloro imine; e) contacting the N-substituted α-chloroimine with a second amine; and f) forming the amidine compound havingonly one N² hydrogen atom.

In an aspect, the present invention relates to a method of preparing anN²-phosphinyl amidine metal salt complex. In an embodiment, the methodof preparing the N²-phosphinyl amidine metal salt complex may comprise:a) contacting a metal salt with an N²-phosphinyl amidine compound; andb) forming the N²-phosphinyl amidine metal salt complex.

In an aspect, the present invention relates to a catalyst systemcomprising a metal salt complexed to a compound having one or moreN²-phosphinyl amidine groups and a metal alkyl. In another aspect,present invention relates to a catalyst system comprising a metal salt,a compound having one or more N²-phosphinyl amidine groups, and a metalalkyl. In an embodiment, the catalyst system may comprise a metal saltcomplexed to a compound having only N²-phosphinyl amidine groups. Insome embodiments, the catalyst system may comprise a metal saltcomplexed to a compound having only two N²-phosphinyl amidine groups. Inan embodiment, the compound may comprise only one N²-phosphinyl amidinegroups. In some embodiments, the compound may comprise only oneN²-phosphinyl amidine group. In an embodiment, the metal salt of themetal complex or the catalyst system may comprise a Group 4-10 metalsalt. In some embodiments, the metal salt of the metal complex or thecatalyst system may comprise chromium. In other embodiments, the metalsalt of the metal complex or the catalyst system may be a chromiumhalide or chromium β-diketonate.

In an aspect, the present invention relates to a method of olefinoligomerization or olefin polymerization. In an embodiment, the methodof olefin oligomerization or olefin polymerization may comprise:contacting an olefin, a catalyst system comprising i) an N²-phosphinylamidine metal salt complex and ii) a metal alkyl, and optionallyhydrogen; and b) forming an olefin oligomer product or olefin polymerproduct. In another embodiment, the method of olefin oligomerization orolefin polymerization may comprise: contacting an olefin, a catalystsystem comprising i) an N²-phosphinyl amidine compound, ii) a metal saltcomplex, and iii) a metal alkyl, and optionally hydrogen; and b) formingan olefin oligomer product or olefin polymer product. In a furtherembodiment, the method of olefin oligomerization or olefinpolymerization may comprise: a) forming a catalyst system mixturecomprising an N²-phosphinyl amidine metal salt complex, a metal alkyl,and a first solvent; b) contacting the catalyst system mixture with anolefin, a second solvent, and optionally hydrogen; and c) forming anolefin oligomer product. In another embodiment, the method of olefinoligomerization or olefin polymerization may comprise: a) forming acomposition comprising an N²-phosphinyl amidine metal salt complex; b)forming a mixture comprising an olefin, a metal alkyl, and optionallyhydrogen; c) contacting the composition of step a) and the mixture ofstep b); and d) forming an olefin oligomer product. In yet anotherembodiment, the method of olefin oligomerization or olefinpolymerization may comprise: a) forming a mixture comprising anN²-phosphinyl amidine compound, a metal salt, a metal alkyl, and a firstsolvent; b) contacting the mixture of step a) with an olefin, a secondsolvent, and optionally hydrogen; and c) forming an olefin oligomerproduct. In a further embodiment, the method of olefin oligomerizationor olefin polymerization may comprise: a) forming a mixture comprisingan N²-phosphinyl amidine compound, a metal salt, and a first solvent; b)forming a mixture comprising an olefin, a metal alkyl, a second solvent,and optionally hydrogen; c) contacting the mixture formed in step a) andthe mixture formed in step b); and d) forming an olefin oligomerproduct.

In an embodiment, the N²-phosphinyl amidine compound or theN²-phosphinyl amidine of the N²-phosphinyl amidine metal salt complexutilized in the method of olefin oligomerization or olefinpolymerization may comprise one or more N²-phosphinyl amidine groups;alternatively, comprise only one N²-phosphinyl amidine group; oralternatively, comprise only two N²-phosphinyl amidine groups. In anembodiment, the metal salt or the metal salt of the N²-phosphinylamidine metal salt complex utilized in the method of olefinoligomerization or olefin polymerization may comprise a Group 4-10 metalsalt; or alternatively, a chromium salt. In some embodiments, the metalsalt or the metal salt of the N²-phosphinyl amidine metal salt complexutilized in the method of olefin oligomerization or olefinpolymerization may comprise a chromium halide or chromium β-diketonate.In an embodiment, the olefin utilized in the method of olefinoligomerization or olefin polymerization may comprise, or consistessentially of, C₂ to C₃₀ olefin; alternatively, C₂ to C₃₀ alpha olefin;alternatively, a C₂ to C₃₀ normal alpha olefin; alternatively, ethyleneor propylene; or alternatively, ethylene. In an embodiment wherein theolefin is ethylene, the olefin oligomerization may be an ethylenetrimerization and/or ethylene tetramerization process. In someembodiments, the olefin trimerization and/or olefin tetramerizationprocess produces an ethylene oligomer product comprising a liquidproduct comprising at least 60 wt. % C₆ and C₈ olefins.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 represents an X-ray of the CrCl₃ Complex B1 recrystallized fromacetonitrile and consequently acetonitrile has displaced tetrahydrofuranin the complex.

DETAILED DESCRIPTION OF THE INVENTION

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997) can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Groups of elements of the table are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances agroup of elements may be indicated using a common name assigned to thegroup; for example alkali earth metals (or alkali metals) for Group 1elements, alkaline earth metals (or alkaline metals) for Group 2elements, transition metals for Group 3-12 elements, and halogens forGroup 17 elements.

Regarding claim transitional terms or phrases, the transitional term“comprising”, which is synonymous with “including,” “containing,”“having,” or “characterized by,” is inclusive or open-ended and does notexclude additional, unrecited elements or method steps. The transitionalphrase “consisting of” excludes any element, step, or ingredient notspecified in the claim. The transitional phrase “consisting essentiallyof” limits the scope of a claim to the specified materials or steps andthose that do not materially affect the basic and novelcharacteristic(s) of the claimed invention. A “consisting essentiallyof” claim occupies a middle ground between closed claims that arewritten in a “consisting of” format and fully open claims that aredrafted in a “comprising” format. Absent an indication to the contrary,when describing a compound or composition “consisting essentially of” isnot to be construed as “comprising,” but is intended to describe therecited component that includes materials which do not significantlyalter the composition or method to which the term is applied. Forexample, a feedstock consisting of a material A can include impuritiestypically present in a commercially produced or commercially availablesample of the recited compound or composition. When a claim includesdifferent features and/or feature classes (for example, a method step,feedstock features, and/or product features, among other possibilities),the transitional terms comprising, consisting essentially of, andconsisting of apply only to the feature class which is utilized and itis possible to have different transitional terms or phrases utilizedwith different features within a claim. For example, a method cancomprise several recited steps (and other non-recited steps) but utilizea catalyst system preparation consisting of specific or alternativelyconsist of specific steps and/or utilize a catalyst system comprisingrecited components and other non-recited components.

While compositions and methods are described in terms of “comprising”various components or steps, the compositions and methods can also“consist essentially of” or “consist of” the various components orsteps.

The terms “a,” “an,” and “the” are intended, unless specificallyindicated otherwise, to include plural alternatives, e.g., at least one.For instance, the disclosure of “a trialkylaluminum compound” is meantto encompass one trialkylaluminum compound, or mixtures or combinationsof more than one trialkylaluminum compound unless otherwise specified.

For any particular compound disclosed herein, the general structure orname presented is also intended to encompass all structural isomers,conformational isomers, and stereoisomers that may arise from aparticular set of substituents, unless indicated otherwise. Thus, ageneral reference to a compound includes all structural isomers unlessexplicitly indicated otherwise; e.g., a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane while ageneral reference to a butyl group includes an n-butyl group, asec-butyl group, an iso-butyl group, and a tert-butyl group.Additionally, the reference to a general structure or name encompassesall enantiomers, diastereomers, and other optical isomers whether inenantiomeric or racemic forms, as well as mixtures of stereoisomers, asthe context permits or requires. For any particular formula or name thatis presented, any general formula or name presented also encompasses allconformational isomers, regioisomers, and stereoisomers that may arisefrom a particular set of substituents.

A chemical “group” is described according to how that group is formallyderived from a reference or “parent” compound, for example, by thenumber of hydrogen atoms formally removed from the parent compound togenerate the group, even if that group is not literally synthesized inthis manner These groups can be utilized as substituents or coordinatedor bonded to metal atoms. By way of example, an “alkyl group” formallycan be derived by removing one hydrogen atom from an alkane, while an“alkylene group” formally can be derived by removing two hydrogen atomsfrom an alkane. Moreover, a more general term can be used to encompass avariety of groups that formally are derived by removing any number (“oneor more”) hydrogen atoms from a parent compound, which in this examplecan be described as an “alkane group,” and which encompasses an “alkylgroup,” an “alkylene group,” and materials have three or more hydrogensatoms, as necessary for the situation, removed from the alkane.Throughout, the disclosure that a substituent, ligand, or other chemicalmoiety may constitute a particular “group” implies that the well-knownrules of chemical structure and bonding are followed when that group isemployed as described. When describing a group as being “derived by,”“derived from,” “formed by,” or “formed from,” such terms are used in aformal sense and are not intended to reflect any specific syntheticmethods or procedure, unless specified otherwise or the context requiresotherwise.

The term “substituted” when used to describe a group, for example, whenreferring to a substituted analog of a particular group, is intended todescribe any non-hydrogen moiety that formally replaces a hydrogen inthat group, and is intended to be non-limiting. A group or groups mayalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.

“Substituted” is intended to be non-limiting and include inorganicsubstituents or organic substituents.

Unless otherwise specified, any carbon-containing group for which thenumber of carbon atoms is not specified can have, according to properchemical practice, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15,16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, or 30 carbonatoms, or any range or combination of ranges between these values. Forexample, unless otherwise specified, any carbon-containing group canhave from 1 to 30 carbon atoms, from 1 to 25 carbon atoms, from 1 to 20carbon atoms, from 1 to 15 carbon atoms, from 1 to 10 carbon atoms, orfrom 1 to 5 carbon atoms, and the like. Moreover, other identifiers orqualifying terms may be utilized to indicate the presence or absence ofa particular substituent, a particular regiochemistry and/orstereochemistry, or the presence or absence of a branched underlyingstructure or backbone.

An amidine group is a group having the general structure

Within the amidine group the nitrogen participating in a double bondwith the central carbon atom is referred to as the N¹ nitrogen and thenitrogen atom participating in a single bond with the central carbonatom is referred to as the N² nitrogen. Similarly, the groups attachedto the N¹ and N² nitrogen atoms are referred to as the N¹ group and N²group respectively. An N²-phosphinyl amidine group has the generalstructure

Within the N²-phosphinyl amidine group the N¹ and N² nitrogen atoms andN¹ and N² groups have the same meaning as described for the amidinegroup. Consequently, an N²-phosphinyl amidine group has the phosphinylgroup is attached to the N² nitrogen atom. Within the amidine group andN²-phosphinyl amidine group the carbon atom between the two nitrogenatoms is the central carbon atom and any substituent attached to it isreferred to as the central carbon group. For the purpose of thisdisclosure and claims, a compound having a pyridine group with a 2-aminegroup (or its analogues—e.g., a pyrimidine ring, an imidazole ring, acompound having 2-aminopyridine group, etc. . . . ) or having a2-phosphinylamine group is not considered to constitute an amidine groupor N²-phosphinyl amidine group, respectively.

The term “organyl group” is used herein in accordance with thedefinition specified by IUPAC: an organic substituent group, regardlessof functional type, having one free valence at a carbon atom. Similarly,an “organylene group” refers to an organic group, regardless offunctional type, derived by removing two hydrogen atoms from an organiccompound, either two hydrogen atoms from one carbon atom or one hydrogenatom from each of two different carbon atoms. An “organic group” refersto a generalized group formed by removing one or more hydrogen atomsfrom carbon atoms of an organic compound. Thus, an “organyl group,” an“organylene group,” and an “organic group” can contain organicfunctional group(s) and/or atom(s) other than carbon and hydrogen, thatis, an organic group can comprise functional groups and/or atoms inaddition to carbon and hydrogen. For instance, non-limiting examples ofatoms other than carbon and hydrogen include halogens, oxygen, nitrogen,phosphorus, and the like. Non-limiting examples of functional groupsinclude ethers, aldehydes, ketones, esters, sulfides, amines,phosphines, and so forth. In one aspect, the hydrogen atom(s) removed toform the “organyl group,” “organylene group,” or “organic group” may beattached to a carbon atom belonging to a functional group, for example,an acyl group (—C(O)R), a formyl group (—C(O)H), a carboxy group(—C(O)OH), a hydrocarboxycarbonyl group (—C(O)OR), a cyano group (—C≡N),a carbamoyl group (—C(O)NH₂), an N-hydrocarbylcarbamoyl group(—C(O)NHR), or N,N′-dihydrocarbylcarbamoyl group (—C(O)NR₂), among otherpossibilities. In another aspect, the hydrogen atom(s) removed to formthe “organyl group,” “organylene group,” or “organic group” may beattached to a carbon atom not belonging to, and remote from, afunctional group, for example, —CH₂C(O)CH₃, —CH₂NR₂, and the like. An“organyl group,” “organylene group,” or “organic group” may bealiphatic, inclusive of being cyclic or acyclic, or may be aromatic.“Organyl groups,” “organylene groups,” and “organic groups” alsoencompass heteroatom-containing rings, heteroatom-containing ringsystems, heteroaromatic rings, and heteroaromatic ring systems. “Organylgroups,” “organylene groups,” and “organic groups” may be linear orbranched unless otherwise specified. Finally, it is noted that the“organyl group,” “organylene group,” or “organic group” definitionsinclude “hydrocarbyl group,” “hydrocarbylene group,” “hydrocarbongroup,” respectively, and “alkyl group,” “alkylene group,” and “alkanegroup,” respectively, as members.

For the purposes of this application, the term or variations of the term“organyl group consisting of inert functional groups” refers to anorganyl group wherein the organic functional group(s) and/or atom(s)other than carbon and hydrogen present in the functional group arerestricted to those functional group(s) and/or atom(s) other than carbonand hydrogen which do not complex with a metal compound and/or are inertunder the process conditions defined herein. Thus, the term or variationof the term “organyl group consisting of inert functional groups”further defines the particular organyl groups that can be present withinthe organyl group consisting of inert functional groups. Additionally,the term “organyl group consisting of inert functional groups” can referto the presence of one or more inert functional groups within theorganyl group. The term or variation of the term “organyl groupconsisting of inert functional groups” definition includes thehydrocarbyl group as a member (among other groups). Similarly, an“organylene group consisting of inert functional groups” refers to anorganic group formed by removing two hydrogen atoms from one or twocarbon atoms of an organic compound consisting of inert functionalgroups and an “organic group consisting of inert functional groups”refers to a generalized organic group consisting of inert functionalgroups formed by removing one or more hydrogen atoms from one or morecarbon atoms of an organic compound consisting of inert functionalgroups.

For purposes of this application, an “inert functional group” is a groupwhich does not substantially interfere with the process described hereinin which the material having an inert functional group takes part and/ordoes not complex with the metal compound of the metal complex. The term“does not complex with the metal compound” may include groups that couldcomplex with a metal compound but in particular molecules describedherein may not complex with a metal compound due to its positionalrelationship within a ligand. For example, while an ether group maycomplex with a metal compound, an ether group located at a para positionof a substituted phenyl phosphinyl group may be an inert functionalgroup because a single metal compound cannot complex with both the paraether group and the N²-phosphinyl amidine group of the same metalcomplex molecule. Thus, the inertness of a particular functional groupis not only related to the functional group's inherent inability tocomplex the metal compound but can also be related to the functionalgroup's position within the metal complex. Non-limiting examples ofinert functional groups which do not substantially interfere withprocesses described herein can include halo (fluoro, chloro, bromo, andiodo), nitro, hydrocarboxy groups (e.g, alkoxy, and/or aroxy, amongothers), sulfidyl groups, and/or hydrocarbyl groups, among others.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen. Otheridentifiers can be utilized to indicate the presence of particulargroups in the hydrocarbon (e.g. halogenated hydrocarbon indicates thatthe presence of one or more halogen atoms replacing an equivalent numberof hydrogen atoms in the hydrocarbon). The term “hydrocarbyl group” isused herein in accordance with the definition specified by IUPAC: aunivalent group formed by removing a hydrogen atom from a hydrocarbon.Non-limiting examples of hydrocarbyl groups include ethyl, phenyl,tolyl, propenyl, and the like. Similarly, a “hydrocarbylene group”refers to a group formed by removing two hydrogen atoms from ahydrocarbon, either two hydrogen atoms from one carbon atom or onehydrogen atom from each of two different carbon atoms. Therefore, inaccordance with the terminology used herein, a “hydrocarbon group”refers to a generalized group formed by removing one or more hydrogenatoms (as necessary for the particular group) from a hydrocarbon. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” canbe acyclic or cyclic groups, and/or may be linear or branched. A“hydrocarbyl group,” “hydrocarbylene group,” and “hydrocarbon group” caninclude rings, ring systems, aromatic rings, and aromatic ring systems,which contain only carbon and hydrogen. “Hydrocarbyl groups,”“hydrocarbylene groups,” and “hydrocarbon groups” include, by way ofexample, aryl, arylene, arene, alkyl, alkylene, alkane, cycloalkyl,cycloalkylene, cycloalkane, aralkyl, aralkylene, and aralkane groups,among other groups, as members.

The term “alkane” whenever used in this specification and claims refersto a saturated hydrocarbon compound. Other identifiers can be utilizedto indicate the presence of particular groups in the alkane (e.g.halogenated alkane indicates that the presence of one or more halogenatoms replacing an equivalent number of hydrogen atoms in the alkane).The term “alkyl group” is used herein in accordance with the definitionspecified by IUPAC: a univalent group formed by removing a hydrogen atomfrom an alkane. Similarly, an “alkylene group” refers to a group formedby removing two hydrogen atoms from an alkane (either two hydrogen atomsfrom one carbon atom or one hydrogen atom from two different carbonatoms). An “alkane group” is a general term that refers to a groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkane. An “alkyl group,” “alkylene group,”and “alkane group” can be acyclic or cyclic groups, and/or may be linearor branched unless otherwise specified. Primary, secondary, and tertiaryalkyl group are derived by removal of a hydrogen atom from a primary,secondary, tertiary carbon atom, respectively, of an alkane. The n-alkylgroup may be derived by removal of a hydrogen atom from a terminalcarbon atom of a linear alkane. The groups RCH₂ (R≠H), R₂CH (R≠H), andR₃C (R≠H) are primary, secondary, and tertiary alkyl groups,respectively.

A cycloalkane is a saturated cyclic hydrocarbon, with or without sidechains, for example, cyclobutane. Unsaturated cyclic hydrocarbons havingone or more endocyclic double or one triple bond are called cycloalkenesand cycloalkynes, respectively. Cycloalkenes and cycloalkynes havingonly one, only two, only three, etc. . . . endocyclic double or triplebonds, respectively, can be identified by use of the term “mono,” “di,”“tri,: etc. . . . within the name of the cycloalkene or cycloalkyne.Cycloalkenes and cycloalkynes can further identify the position of theendocyclic double or triple bonds.

A “cycloalkyl group” is a univalent group derived by removing a hydrogenatom from a ring carbon atom of a cycloalkane. For example, a1-methylcyclopropyl group and a 2-methylcyclopropyl group areillustrated as follows.

Similarly, a “cycloalkylene group” refers to a group derived by removingtwo hydrogen atoms from a cycloalkane, at least one of which is a ringcarbon. Thus, a “cycloalkylene group” includes both a group derived froma cycloalkane in which two hydrogen atoms are formally removed from thesame ring carbon, a group derived from a cycloalkane in which twohydrogen atoms are formally removed from two different ring carbons, anda group derived from a cycloalkane in which a first hydrogen atom isformally removed from a ring carbon and a second hydrogen atom isformally removed from a carbon atom that is not a ring carbon. A“cycloalkane group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is a ring carbon) from a cycloalkane. It should benoted that according to the definitions provided herein, generalcycloalkane groups (including cycloalkyl groups and cycloalkylenegroups) include those having zero, one, or more than one hydrocarbylsubstituent groups attached to a cycloalkane ring carbon atom (e.g. amethylcyclopropyl group) and is member of the group of hydrocarbongroups. However, when referring to a cycloalkane group having aspecified number of cycloalkane ring carbon atoms (e.g. cyclopentanegroup or cyclohexane group, among others), the base name of thecycloalkane group having a defined number of cycloalkane ring carbonatoms refers to the unsubstituted cycloalkane group (including having nohydrocarbyl groups located on cycloalkane group ring carbon atom).Consequently, a substituted cycloalkane group having a specified numberof ring carbon atoms (e.g. substituted cyclopentane or substitutedcyclohexane, among others) refers to the respective group having one ormore substituent groups (including halogens, hydrocarbyl groups, orhydrocarboxy groups, among other substituent groups) attached to acycloalkane group ring carbon atom. When the substituted cycloalkanegroup having a defined number of cycloalkane ring carbon atoms is amember of the group of hydrocarbon groups (or a member of the generalgroup of cycloalkane groups), each substituent of the substitutedcycloalkane group having a defined number of cycloalkane ring carbonatoms is limited to hydrocarbyl substituent group. One can readilydiscern and select general groups, specific groups, and/or individualsubstituted cycloalkane group(s) having a specific number of ringcarbons atoms which can be utilized as member of the hydrocarbon group(or a member of the general group of cycloalkane groups).

The term “olefin” whenever used in this specification and claims refersto compounds that have at least one carbon-carbon double bond that isnot part of an aromatic ring or ring system. The term “olefin” includesaliphatic and aromatic, cyclic and cyclic, and/or linear and branchedcompounds having at least one carbon-carbon double bond that is not partof an aromatic ring or ring system unless specifically stated otherwise.The term “olefin,” by itself, does not indicate the presence or absenceof heteroatoms and/or the presence or absence of other carbon-carbondouble bonds unless explicitly indicated. Olefins having only one, onlytwo, only three, etc. . . . carbon-carbon double bonds can be identifiedby use of the term “mono,” “di,” “tri,” etc. . . . within the name ofthe olefin. The olefins can be further identified by the position of thecarbon-carbon double bond(s).

The term “alkene” whenever used in this specification and claims refersa linear or branched hydrocarbon olefin that has one or morecarbon-carbon double bonds. Alkenes having only one, only two, onlythree, etc. . . . such multiple bond can be identified by use of theterm “mono,” “di,” “tri,” etc. . . . within the name. For example,alkamonoenes, alkadienes, and alkatrienes refer to a linear or branchedhydrocarbon olefins having only one carbon-carbon double bond (generalformula C_(n)H_(2n)), only two carbon-carbon double bonds (generalformula C_(n)H_(2n-2)), and only three carbon-carbon double bonds(general formula C_(n)H_(2n-4)), respectively. Alkenes can be furtheridentified by the position of the carbon-carbon double bond(s). Otheridentifiers can be utilized to indicate the presence or absence ofparticular groups within an alkene. For example, a haloalkene refers toan alkene having one or more hydrogen atoms replace with a halogen atom.

An “alkenyl group” is a univalent group derived from an alkene byremoval of a hydrogen atom from any carbon atom of the alkene. Thus,“alkenyl group” includes groups in which the hydrogen atom is formallyremoved from an sp² hybridized (olefinic) carbon atom and groups inwhich the hydrogen atom is formally removed from any other carbon atom.For example and unless otherwise specified, 1-propenyl (—CH═CHCH₃),2-propenyl [(CH₃)C═CH₂], and 3-propenyl (—CH₂CH═CH₂) groups are allencompassed with the term “alkenyl group.” Similarly, an “alkenylenegroup” refers to a group formed by formally removing two hydrogen atomsfrom an alkene, either two hydrogen atoms from one carbon atom or onehydrogen atom from two different carbon atoms. An “alkene group” refersto a generalized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from an alkene. When the hydrogenatom is removed from a carbon atom participating in a carbon-carbondouble bond, the regiochemistry of the carbon from which the hydrogenatom is removed, and regiochemistry of the carbon-carbon double bond mayboth be specified. Alkene groups can also have more than onecarbon-carbon double bond. Alkene groups can also be further identifiedby the position of the carbon-carbon double bond.

The term “alkyne” whenever used in this specification and claims refersa linear or branched hydrocarbon olefin that has one or morecarbon-carbon triple bonds. Alkynes having only one, only two, onlythree, etc. . . . such multiple bond can be identified by use of theterm “mono,” “di,” “tri,”: etc. . . . within the name. For example,alkamonoynes, alkadiynes, and alkatriynes refer to a linear or branchedhydrocarbon olefins having only one carbon-carbon triple bond (generalformula C_(n)H_(2n-2)), only two carbon-carbon triple bonds (generalformula C_(n)H_(2n-6)), and only three carbon-carbon triple bonds(general formula C_(n)H_(2n-10)), respectively. Alkynes can be furtheridentified by the position of the carbon-carbon triple bond(s). Otheridentifiers can be utilized to indicate the presence or absence ofparticular groups within an alkyne. For example, a haloalkyne refers toan alkyne having one or more hydrogen atoms replace with a halogen atom.

An “alkynyl group” is a univalent group derived from an alkyne byremoval of a hydrogen atom from any carbon atom of the alkyne. Thus,“alkynyl group” includes groups in which the hydrogen atom is formallyremoved from an sp hybridized (acetylenic) carbon atom and groups inwhich the hydrogen atom is formally removed from any other carbon atom.For example and unless otherwise specified, 1-propynyl (—C≡CCH₃) and3-propynyl (HC≡CCH₂—) groups are all encompassed with the term “alkynylgroup.” Similarly, an “alkynylene group” refers to a group formed byformally removing two hydrogen atoms from an alkyne, either two hydrogenatoms from one carbon atom if possible or one hydrogen atom from twodifferent carbon atoms. An “alkyne group” refers to a generalized groupformed by removing one or more hydrogen atoms (as necessary for theparticular group) from an alkyne. Other identifiers may be utilized toindicate the presence or absence of particular groups within an alkynegroup. Alkyne groups can also have more than one carbon carbon triplebond. Alkyne groups can also be further identified by the position ofthe carbon-carbon triple bond.

The term “alpha olefin” as used in this specification and claims refersto an olefin that has a carbon-carbon double bond between the first andsecond carbon atom of the longest contiguous chain of carbon atoms. Theterm “alpha olefin” includes linear and branched alpha olefins unlessexpressly stated otherwise. In the case of branched alpha olefins, abranch may be at the 2-position (a vinylidene) and/or the 3-position orhigher with respect to the olefin double bond. The term “vinylidene”whenever used in this specification and claims refers to an alpha olefinhaving a branch at the 2-position with respect to the olefin doublebond. By itself, the term “alpha olefin” does not indicate the presenceor absence of heteroatoms and/or the presence or absence of othercarbon-carbon double bonds unless explicitly indicated. The terms“hydrocarbon alpha olefin” or “alpha olefin hydrocarbon” refer to alphaolefin compounds containing only hydrogen and carbon.

The term “linear alpha olefin” as used herein refers to a linear olefinhaving a carbon-carbon double bond between the first and second carbonatom. The term “linear alpha olefin” by itself does not indicate thepresence or absence of heteroatoms and/or the presence or absence ofother carbon-carbon double bonds, unless explicitly indicated. The terms“linear hydrocarbon alpha olefin” or “linear alpha olefin hydrocarbon”refers to linear alpha olefin compounds containing only hydrogen andcarbon.

The term “normal alpha olefin” whenever used in this specification andclaims refers to a linear hydrocarbon mono-olefin having a carbon carbondouble bond between the first and second carbon atom. It is noted that“normal alpha olefin” is not synonymous with “linear alpha olefin” asthe term “linear alpha olefin” can include linear olefinic compoundshaving a double bond between the first and second carbon atoms andhaving heteroatoms and/or additional double bonds.

The term “consists essentially of normal alpha olefin(s),” or variationsthereof, whenever used in this specification and claims refers tocommercially available normal alpha olefin product(s). The commerciallyavailable normal alpha olefin product can contain non-normal alphaolefin impurities such as vinylidenes, internal olefins, branched alphaolefins, paraffins, and diolefins, among other impurities, which are notremoved during the normal alpha olefin production process. One readilyrecognizes that the identity and quantity of the specific impuritiespresent in the commercial normal alpha olefin product will depend uponthe source of commercial normal alpha olefin product. Consequently, theterm “consists essentially of normal alpha olefins” and its variants isnot intended to limit the amount/quantity of the non-linear alpha olefincomponents any more stringently than the amounts/quantities present in aparticular commercial normal alpha olefin product unless explicitlystated.

A “heterocyclic compound” is a cyclic compound having at least twodifferent elements as ring member atoms. For example, heterocycliccompounds may comprise rings containing carbon and nitrogen (forexample, tetrahydropyrrole), carbon and oxygen (for example,tetrahydrofuran), or carbon and sulfur (for example,tetrahydrothiophene), among others. Heterocyclic compounds andheterocyclic groups may be either aliphatic or aromatic.

A “heterocyclyl group” is a univalent group formed by removing ahydrogen atom from a heterocyclic ring or ring system carbon atom of aheterocyclic compound. By specifying that the hydrogen atom is removedfrom a heterocyclic ring or ring system carbon atom, a “heterocyclylgroup” is distinguished from a “cycloheteryl group,” in which a hydrogenatom is removed from a heterocyclic ring or ring system heteroatom. Forexample, a pyrrolidin-2-yl group illustrated below is one example of a“heterocyclyl group,” and a pyrrolidin-1-yl group illustrated below isone example of a “cycloheteryl” group.”

Similarly, a “heterocyclylene group” or more simply, a “heterocyclenegroup,” refers to a group formed by removing two hydrogen atoms from aheterocyclic compound, at least one of which is from a heterocyclic ringor ring system carbon. Thus, in a “heterocyclylene group,” at least onehydrogen is removed from a heterocyclic ring or ring system carbon atom,and the other hydrogen atom can be removed from any other carbon atom,including for example, the same heterocyclic ring or ring system carbonatom, a different heterocyclic ring or ring system ring carbon atom, ora non-ring carbon atom. A “heterocyclic group” refers to a generalizedgroup formed by removing one or more hydrogen atoms (as necessary forthe particular group and at least one of which is a heterocyclic ringcarbon atom) from a heterocyclic compound. Generally, a heterocycliccompound may be aliphatic or aromatic unless otherwise specified.

A “cycloheteryl group” is a univalent group formed by removing ahydrogen atom from a heterocyclic ring or ring system heteroatom of aheterocyclic compound, as illustrated. By specifying that the hydrogenatom is removed from a heterocyclic ring or ring system heteroatom andnot from a ring carbon atom, a “cycloheteryl group” is distinguishedfrom a “heterocyclyl group” in which a hydrogen atom is removed from aheterocyclic ring or ring system carbon atom. Similarly, a“cycloheterylene group” refers to a group formed by removing twohydrogen atoms from an heterocyclic compound, at least one of which isremoved from a heterocyclic ring or ring system heteroatom of theheterocyclic compound; the other hydrogen atom can be removed from anyother atom, including for example, a heterocyclic ring or ring systemring carbon atom, another heterocyclic ring or ring system heteroatom,or a non-ring atom (carbon or heteroatom). A “cyclohetero group” refersto a generalized group formed by removing one or more hydrogen atoms (asnecessary for the particular group and at least one of which is from aheterocyclic ring or ring system heteroatom) from a heterocycliccompound.

An aliphatic compound is an acyclic or cyclic, saturated or unsaturatedcarbon compound, excluding aromatic compounds. Thus, an aliphaticcompound is an acyclic or cyclic, saturated or unsaturated carboncompound, excluding aromatic compounds; that is, an aliphatic compoundis a non-aromatic organic compound. An “aliphatic group” is ageneralized group formed by removing one or more hydrogen atoms (asnecessary for the particular group) from the carbon atom of an aliphaticcompound. Thus, an aliphatic compound is an acyclic or cyclic, saturatedor unsaturated carbon compound, excluding aromatic compounds. That is,an aliphatic compound is a non-aromatic organic compound. Aliphaticcompounds and therefore aliphatic groups may contain organic functionalgroup(s) and/or atom(s) other than carbon and hydrogen.

An aromatic compound is a compound containing a cyclically conjugateddouble bond system that follows the Hückel (4n+2) rule and contains(4n+2) pi-electrons, where n is an integer from 1 to 5. Aromaticcompounds include “arenes” (hydrocarbon aromatic compounds) and“heteroarenes,” also termed “hetarenes” (heteroaromatic compoundsformally derived from arenes by replacement of one or more methine (—C═)carbon atoms of the cyclically conjugated double bond system with atrivalent or divalent heteroatoms, in such a way as to maintain thecontinuous pi-electron system characteristic of an aromatic system and anumber of out-of-plane pi-electrons corresponding to the Hückel rule(4n+2). While arene compounds and heteroarene compounds are mutuallyexclusive members of the group of aromatic compounds, a compound thathas both an arene group and a heteroarene group are generally considereda heteroarene compound. Aromatic compounds, arenes, and heteroarenes canbe monocyclic (e.g., benzene, toluene, furan, pyridine, methylpyridine)or polycyclic unless otherwise specified. Polycyclic aromatic compounds,arenes, and heteroarenes, include, unless otherwise specified, compoundswherein the aromatic rings can be fused (e.g., naphthalene, benzofuran,and indole), compounds where the aromatic groups can be separate andjoined by a bond (e.g., biphenyl or 4-phenylpyridine), or compoundswhere the aromatic groups are joined by a group containing linking atoms(e.g., carbon—the methylene group in diphenylmethane; oxygen—diphenylether; nitrogen—triphenyl amine; among others linking groups). Asdisclosed herein, the term “substituted” can be used to describe anaromatic group, arene, or heteroarene wherein a non-hydrogen moietyformally replaces a hydrogen in the compound, and is intended to benon-limiting.

An “aromatic group” refers to a generalized group formed by removing oneor more hydrogen atoms (as necessary for the particular group and atleast one of which is an aromatic ring carbon atom) from an aromaticcompound. For a univalent “aromatic group,” the removed hydrogen atommust be from an aromatic ring carbon. For an “aromatic group” formed byremoving more than one hydrogen atom from an aromatic compound, at leastone hydrogen atom must be from an aromatic hydrocarbon ring carbon.Additionally, an “aromatic group” may have hydrogen atoms removed fromthe same ring of an aromatic ring or ring system (e.g., phen-1,4-ylene,pyridin-2,3-ylene, naphth-1,2-ylene, and benzofuran-2,3-ylene), hydrogenatoms removed from two different rings of a ring system (e.g.,naphth-1,8-ylene and benzofuran-2,7-ylene), or hydrogen atoms removedfrom two isolated aromatic rings or ring systems (e.g.,bis(phen-4-ylene)methane).

An arene is aromatic hydrocarbon, with or without side chains (e.g.benzene, toluene, or xylene, among others. An “aryl group” is a groupderived from the formal removal of a hydrogen atom from an aromatic ringcarbon of an arene. It should be noted that the arene may contain asingle aromatic hydrocarbon ring (e.g., benzene, or toluene), containfused aromatic rings (e.g., naphthalene or anthracene), and contain oneor more isolated aromatic rings covalently linked via a bond (e.g.,biphenyl) or non-aromatic hydrocarbon group(s) (e.g., diphenylmethane).One example of an “aryl group” is ortho-tolyl (o-tolyl), the structureof which is shown here.

Similarly, an “arylene group” refers to a group formed by removing twohydrogen atoms (at least one of which is from an aromatic ring carbon)from an arene. An “arene group” refers to a generalized group formed byremoving one or more hydrogen atoms (as necessary for the particulargroup and at least one of which is an aromatic ring carbon) from anarene. However, if a group contains separate and distinct arene andheteroarene rings or ring systems (e.g. the phenyl and benzofuranmoieties in 7-phenylbenzofuran) its classification depends upon theparticular ring or ring system from which the hydrogen atom was removed,that is, an arene group if the removed hydrogen came from the aromatichydrocarbon ring or ring system carbon atom (e.g. the 2 carbon atom inthe phenyl group of 6-phenylbenzofuran and a heteroarene group if theremoved hydrogen carbon came from a heteroaromatic ring or ring systemcarbon atom (e.g. the 2 or 7 carbon atom of the benzofuran group or6-phenylbenzo-furan). It should be noted that according the definitionsprovided herein, general arene groups (including an aryl group and anareylene group) include those having zero, one, or more than onehydrocarbyl substituent groups located on an aromatic hydrocarbon ringor ring system carbon atom (e.g a toluene group or a xylene group, amongothers) and is a member of the group of hydrocarbon groups. However, aphenyl group (or phenylene group) and/or a naphthyl group (ornaphthylene group) refer to the specific unsubstituted arene groups(including no hydrocarbyl group located on an aromatic hydrocarbon ringor ring system carbon atom). Consequently, a substituted phenyl group orsubstituted naphthyl group refers to the respective arene group havingone or more substituent groups (including halogens, hydrocarbyl groups,or hydrocarboxy groups, among others) located on an aromatic hydrocarbonring or ring system carbon atom. When the substituted phenyl groupand/or substituted naphtyl group is a member of the group of hydrocarbongroups (or a member of the general group of arene groups), eachsubstituent is limited to a hydrocarbyl substituent group. One havingordinary skill in the art can readily discern and select general phenyland/or naphthyl groups, specific phenyl and/or naphthyl groups, and/orindividual substituted phenyl or substituted naphthyl groups which canbe utilized as a member of the group of hydrocarbon groups (or a memberof the general group of arene groups).

A heteroarene is aromatic compound, with or without side chains, havinga heteroatom within the aromatic ring or aromatic ring system (e.g.pyridene, indole, or benzofuran, among others). A “heteroaryl group” isa class of “heterocyclyl group” and is a univalent group formed byremoving a hydrogen atom from a heteroaromatic ring or ring systemcarbon atom of a heteroarene compound. By specifying that the hydrogenatom is removed from a ring carbon atom, a “heteroaryl group” isdistinguished from an “arylheteryl group,” in which a hydrogen atom isremoved from a heteroaromatic ring or ring system heteroatom. Forexample, an indol-2-yl group illustrated below is one example of a“heteroaryl group,” and an indol-1-yl group illustrated below is oneexample of an “arylheteryl” group.”

Similarly, a “heteroarylene group” refers to a group formed by removingtwo hydrogen atoms from a heteroarene compound, at least one of which isfrom a heteroarene ring or ring system carbon atom. Thus, in a“heteroarylene group,” at least one hydrogen is removed from aheteroarene ring or ring system carbon atom, and the other hydrogen atomcan be removed from any other carbon atom, including for example, aheteroarene ring or ring system carbon atom, or a non-heteroarene ringor ring system atom. A “heteroarene group” refers to a generalized groupformed by removing one or more hydrogen atoms (as necessary for theparticular group and at least one of which is a heteroarene ring or ringsystem carbon atom) from a heteroarene compound. If a hydrogen atom isremoved from a heteroaromatic ring or ring system heteroatom and from aheteroaromatic ring or ring system carbon atom or an aromatichydrocarbon ring or ring system carbon atom, the group is classified asan “arylheterylene group” or an “arylhetero group.”

An “arylheteryl group” is a class of “cycloheteryl group” and is aunivalent group formed by removing a hydrogen atom from a heteroaromaticring or ring system heteroatom, as illustrated. By specifying that thehydrogen atom is removed from of a heteroaromatic ring or ring systemheteroatom and not from a heteroaromatic ring or ring system carbonatom, an “arylheteryl group” is distinguished from a “heteroaryl group”in which a hydrogen atom is removed from a heteroaromatic ring or a ringsystem carbon atom. Similarly, an “arylheterylene group” refers to agroup formed by removing two hydrogen atoms from a heteroaryl compound,at least one of which is removed from a heteroaromatic ring or ringsystem heteroatom of the heteroaryl compound; the other hydrogen atomcan be removed from any other atom, including for example, aheteroaromatic ring or ring system carbon atom, another heteroaromaticring or ring system heteroatom, or a non-ring atom (carbon orheteroatom) from a heteroaromatic compound. An “arylhetero group” refersto a generalized group formed by removing one or more hydrogen atoms (asnecessary for the particular group and at least one of which is from aheteroaromatic ring or ring system) heteroatom from a heteroarenecompound.

An “aralkyl group” is an aryl-substituted alkyl group having a freevalance at a non-aromatic carbon atom (e.g. a benzyl group, or a2-phenyleth-1yl group, among others). Similarly, an “aralkylene group”is an aryl-substituted alkylene group having two free valencies at asingle non-aromatic carbon atom or a free valence at two non-aromaticcarbon atoms while an “aralkane group” is a generalized is anaryl-substituted alkane group having one or more free valencies at anon-aromatic carbon atom(s). A “heteroaralkyl group” is aheteroaryl-substituted alkyl group having a free valence at anon-heteroaromatic ring or ring system carbon atom. Similarly a“heteroaralkylene group” is a heteroaryl-substituted alkylene grouphaving two free valencies at a single non-heteroaromatic ring or ringsystem carbon atom or a free valence at two non-heteroaromatic ring orring system carbon atoms while a “heteroaralkane group” is a generalizedaryl-substituted alkane group having one or more free valencies at anon-heteroaromatic ring or ring system carbon atom(s). It should benoted that according the definitions provided herein, general aralkanegroups include those having zero, one, or more than one hydrocarbylsubstituent groups located on an aralkane aromatic hydrocarbon ring orring system carbon atom and is a member of the group of hydrocarbongroups. However, specific aralkane groups specifying a particular arylgroup (e.g. the phenyl group in a benzyl group or a 2-phenylethyl group,among others) refer to the specific unsubstituted aralkane groups(including no hydrocarbyl group located on the aralkane aromatichydrocarbon ring or ring system carbon atom). Consequently, asubstituted aralkane group specifying a particular aryl group refers toa respective aralkane group having one or more substituent groups(including halogens, hydrocarbyl groups, or hydrocarboxy groups, amongothers). When the substituted aralkane group specifying a particulararyl group is a member of the group of hydrocarbon groups (or a memberof the general group of aralkane groups), each substituent is limited toa hydrocarbyl substituent group. One can readily discern and selectsubstituted aralkane groups specifying a particular aryl group which canbe utilized as a member of the group of hydrocarbon groups (or a memberof the general group of aralkane groups).

A “halide” has its usual meaning; therefore, examples of halides includefluoride, chloride, bromide, and iodide.

An “organoheteryl group” is a univalent group containing carbon, whichare thus organic, but which have their free valence at an atom otherthan carbon. Thus, organoheteryl and organyl groups are complementaryand mutually exclusive. Organoheteryl groups can be cyclic or acyclic,and/or aliphatic or aromatic, and thus encompasses aliphatic“cycloheteryl groups” (e.g. pyrrolidin-1-yl or morpholin-1-yl, amongothers), aromatic “arylheteryl groups” (e.g. pyrrol-1-yl or indol-1-yl,among others), and acyclic groups (e.g. organylthio,trihydrocarbylsilyl, aryloxy, or alkoxy, among others). Similarly, an“organoheterylene group” is a divalent group containing carbon and atleast one heteroatom having two free valencies, at least one of which isat a heteroatom. An “organohetero group” is a generalized groupcontaining carbon and at least one heteroatom having one or more freevalencies (as necessary for the particular group and at least one ofwhich is at a heteroatom) from an organohetero compound.

An “oxygen group,” also called an “oxygen-bonded group,” is a chemicalmoiety having at least one free valence on an oxygen atom. Exemplary“oxygen groups” include, but are not limited to, hydroxy (—OH), —OR,—OC(O)R, —OSiR₃, —OPR₂, —OAlR₂, —OSiR₂, —OGeR₃, —OSnR₃, —OSO₂R, —OSO₂OR,—OBR₂, —OB(OR)₂, —OAlR₂, —OGaR₂, —OP(O)R₂, —OAs(O)R₂, —OAlR₂, and thelike, including substituted analogs thereof. In an “oxygen group” havingmore than one free valency, the other free valencies may be on atom(s)other than oxygen, for example carbon, in accord with the rules ofchemical structure and bonding.

A “sulfur group,” also called a “sulfur-bonded group,” is a chemicalmoiety having at least one free valence on a sulfur atom. Exemplary“sulfur group(s)” include, but are not limited to, —SR, —SCN, —S(O)R,—SO₂R, and the like, including substituted analogs thereof. In a “sulfurgroup” having more than one free valency, the other free valencies maybe on atom(s) other than sulfur, for example carbon, in accord with therules of chemical structure and bonding.

A “nitrogen group,” also called a “nitrogen-bonded group,” is a chemicalmoiety having at least one free valence on a nitrogen atom. Exemplary“nitrogen groups” include, but are not limited to, an aminyl group(—NH₂), an N-substituted aminyl group (—NRH), an N,N-disubstitutedaminyl group (—NR₂), a hydrazido group (—NHNH₂), an N¹-substitutedhydrazido group (—NRNH₂), an N²-substituted hydrazido group (—NHNRH), anN²,N²-disubstituted hydrazido group (—NHNR₂), a nitro group (—NO₂), anazido group (—N₃), an amidyl group (—NHC(O)R), an N-substituted amidogroup (—NRC(O)R), and the like, including substituted analogs thereof.In a “nitrogen group” having more than one free valency, the other freevalencies may be on any atom(s) in the group in accord with the rules ofchemical structure and bonding, including atoms other than nitrogen, forexample, carbon.

A “phosphorus group,” also called a “phosphorus-bonded group,” is achemical moiety having at least one free valence on a phosphorus atom.Exemplary “phosphorous groups include, but are not limited to, —PR₂,—P(O)R₂, —P(OR)₂, —P(O)(OR)₂, —P(NR₂)₂, —P(O)(NR₂)₂, and the like,including substituted analogs thereof. In a “phosphorus group” havingmore than one free valency, the other free valencies may be on anyatom(s) in the group in accord with the rules of chemical structure andbonding, including atoms other than phosphorus, for example, carbon.

For each of the specific groups in which the free valency is situated ona heteroatom (non-carbon atom), such as the “oxygen group,” “sulfurgroup,” “nitrogen group,” “phosphorus group,” can include a general “R”moiety. In each instance and unless other wise specified, R in a “oxygengroup,” “sulfur group,” “nitrogen group,” “phosphorus group,” can be aC₁ to C₂₀ organyl group; alternatively, a C₁ to C₂₀ hydrocarbyl group;alternatively, a C₁ to C₂₀ alkyl group; alternatively, a C₁ to C₂₀aliphatic group; alternatively, a C₁ to C₂₀ cycloalkyl group;alternatively, a C₁ to C₂₀ alkenyl group; alternatively, a C₁ to C₂₀alkynyl group; alternatively, a C₄ to C₂₀ aromatic group; alternatively,C₆ to C₂₀ an aryl group; alternatively, a C₃ to C₂₀ heterocyclyl group;alternatively, a C₃ to C₂₀ cycloheteryl group; alternatively, a C₃ toC₂₀ heteroaryl group; alternatively, an C₃ to C₂₀ arylheteryl group;alternatively, an C₁ to C₂₀ organoheteryl group; alternatively, an C₇ toC₂₀ aralkyl group; or alternatively, a C₅ to C₂₀ heteroaralkyl group.

An “organoaluminum compound,” is used to describe any compound thatcontains an aluminum-carbon bond. Thus, organoaluminum compounds includehydrocarbyl aluminum compounds such as trialkyl-, dialkyl-, ormonoalkylaluminum compounds; hydrocarbyl alumoxane compounds, andaluminate compounds which contain an aluminum-organyl bond such astetrakis(p-tolyl)aluminate salts.

Within this disclosure the normal rules of organic nomenclature willprevail. For instance, when referencing substituted compounds or groups,references to substitution patterns are taken to indicate that theindicated group(s) is (are) located at the indicated position and thatall other non-indicated positions are hydrogen. For example, referenceto a 4-substituted phenyl group indicates that there is a non-hydrogensubstituent located at the 4 position and hydrogens located at the 2, 3,5, and 6 positions. By way of another example, reference to a3-subtituted naphth-2-yl indicates that there is a non-hydrogensubstituent located at the 3 position and hydrogens located at the 1, 4,5, 6, 7, and 8 positions. References to compounds or groups havingsubstitutions at positions in addition to the indicated position will bereference using comprising or some other alternative language. Forexample, a reference to a phenyl group comprising a substituent at the 4position refers to a group having a non-hydrogen atom at the 4 positionand hydrogen or any non-hydrogen group at the 2, 3, 5, and 6 positions.

The term “reactor effluent,” and it derivatives (e.g. oligomerizationreactor effluent) generally refers to all the material which exits thereactor. The term “reactor effluent,” and its derivatives, can also beprefaced with other descriptors that limit the portion of the reactoreffluent being referenced. For example, while the term “reactoreffluent” would refer to all material exiting the reactor (e.g. productand solvent or diluent, among others), the term “olefin reactoreffluent” refers to the effluent of the reactor which contains an olefin(i.e. carbon-carbon) double bond.

The term “oligomerization,” and its derivatives, refers to processeswhich produce a mixture of products containing at least 70 weightpercent products containing from 2 to 30 monomer units. Similarly, an“oligomer” is a product that contains from 2 to 30 monomer units whilean “oligomerization product” includes all product made by the“oligomerization” process including the “oligomers” and products whichare not “oligomers” (e.g. product which contain more than 30 monomerunits). It should be noted that the monomer units in the “oligomer” or“oligomerization product” do not have to be the same. For example, an“oligomer” or “oligomerization product” of an “oligomerization” processusing ethylene and propylene as monomers can contain both ethyleneand/or propylene units.

The term “trimerization,” and it derivatives, refers to a process whichproduces a mixture of products containing at least 70 weight percentproducts containing three and only three monomer units. A “trimer” is aproduct which contains three and only three monomer units while a“trimerization product” includes all products made by the trimerizationprocess including trimer and product which are not trimer (e.g. dimersor tetramers). Generally, an olefin trimerization reduces number ofolefinic bonds, i.e., carbon-carbon double bonds, by two whenconsidering the number of olefin bonds in the monmer units and thenumber of olefin bonds in the trimer. It should be noted that themonomer units in the “trimer” or “trimerization product” do not have bethe same. For example, a “trimer” of a “trimerization” process usingethylene and butene as monomers can contain ethylene and/or butenemonomer units. That is to say the “trimer” will include C₆, C₈, C₁₀, andC₁₂ products. In another example, a “trimer” of a “trimerization”process using ethylene as the monomer can contain ethylene monomerunits. It should also be noted that a single molecule can contain twomonomer units. For example, dienes such as 1,3-butadiene and1,4-pentadiene have two monomer units within one molecule.

The term “tetramerization,” and it derivatives, refers to a processwhich produces a mixture of products containing at least 70 weightpercent products containing four and only four monomer units. A“tetramer” is a product which contains four and only four monomer unitswhile a “tetramerization product” includes all products made by thetetramerization process including tetramer and product which are nottetramer (e.g. dimers or trimer). Generally, an olefin tetramerizationreduces number of olefinic bonds, i.e., carbon-carbon double bonds, bythree when considering the number of olefin bonds in the monmer unitsand the number of olefin bonds in the tetramer. It should be noted thatthe monomer units in the “tetramer” or “tetramerization product” do nothave be the same. For example, a “tetramer” of a “tetramerization”process using ethylene and butene as monomers can contain ethyleneand/or butene monomer units. In an example, a “tetramer” of a“tetramerization” process using ethylene as the monomer can containethylene monomer units. It should also be noted that a single moleculecan contain two monomer units. For example, dienes such as 1,3-butadieneand 1,4-pentadiene have two monomer units within one molecule.

The term “trimerization and tetramerization,” and it derivatives, refersto a process which produces a mixture of products containing at least 70weight percent products containing three and/or four and only threeand/or four monomer units. A “trimerization and tetramerization product”includes all products made by the “trimerization and tetramerization”process including trimer, tetramer, and product which are not tetramer(e.g. dimers). In an example, a “trimerization and tetramerization”process using ethylene as the monomer produces a mixture of productscontaining at least 70 weight percent hexene and/or octene.

The term or variation of the terms an “oligomerized product having Xcarbon atoms” and “C_(x) oligomer product,” wherein X can be anypositive non-zero integer, refers to materials produced by monomeroligomerization which have X carbon atoms. Thus, the term oligomerizedproduct having X carbon atoms excludes materials having X carbon atomswhich were not produced by the olefin oligomerization (e.g. solvent).These terms can also include other descriptive words (e.g. olefin,liquid, and mixture, among others) without detracting from the essenceof the term referring to materials having X carbon atoms, produced bymonomer oligomerization, and fitting the additional descriptive terms.

Catalyst system activity is defined as grams of a product produced pergram of metal of the metal salt or the N²-phosphinyl amidine metal saltcomplex utilized in the catalyst system over the first 30 minutes of anoligomerization or polymerization reaction beginning from the time whenthe complete catalyst system is contacted with the olefin. Catalystsystem activity can be stated in terms of various products of an olefinoligomerization or polymerization. For example in an ethylenetrimerization and tetramerization process utilizing a chromium basedcatalyst system, catalyst system activities which can be utilizedinclude (g C₆)/(g Cr), (g C₈)/(g Cr), (C₆+C₈)/(g Cr), (g ethyleneoligomer)/(g Cr), and (total product)/(g Cr), among other activities.

This disclosure encompasses N²-phosphinyl amidine compounds, methods formaking N²-phosphinyl amidine compounds, metal salt complexes comprisingN²-phosphinyl amidine compounds, methods of making metal salt complexescomprising N²-phosphinyl amidine compounds, catalyst systems comprisingN²-phosphinyl amidine compounds, methods of making catalyst systemscomprising N²-phosphinyl amidine compounds, and methods of oligomerizingolefins utilizing catalysts system comprising N²-phosphinyl amidinecompounds, among other aspects an embodiments. These aspects of thisdisclosure are further described herein. While these aspects may bedisclosed under these headings, the heading does not limit thedisclosure found therein. Additionally the various aspects andembodiments disclosed herein can be combined in any manner.

Generally, the N²-phosphinyl amidine compounds encompassed by thisdisclosure have at least one N²-phosphinyl amidine group. In anembodiment, the N²-phosphinyl amidine compounds comprise only oneN²-phosphinyl amidine; or alternatively, comprise only two N²-phosphinylamidine groups.

In an aspect, the compounds encompassed by the present disclosureinclude an N²-phosphinyl amidine compound. Generally, the N²-phosphinylamidine compounds encompassed by this disclosure comprise anN²-phosphinyl amidine group; or alternatively, comprise twoN²-phosphinyl amidine groups. In an embodiment, the N²-phosphinylamidine compounds comprise only one N²-phosphinyl amidine group; oralternatively, comprise only two N²-phosphinyl amidine groups. In anembodiment, the compounds, regardless of the number of N²-phosphinylamidine groups, or structure, can be non-metallic (i.e., a non-metallicN²-phosphinyl amidine compound or a non-metallic compound having anN²-phosphinyl amidine group). In some embodiments, the amidine group ofthe N²-phosphinyl amidine compounds is an acyclic amidine group (anamidine group wherein the two nitrogen atoms and the central carbon atomof the amine group are not contained in a ring).

In an aspect, the N²-phosphinyl amidine compound may have Structure NP1,NP2, NP3, NP4, NP5, NP6, NP7, NP8, NP9, NP10, NP11, NP13, NP15, NP16,NP18, or NP20; alternatively, Structure NP1, NP2, NP3, NP4, or NP5;alternatively, NP6, NP7, NP8, NP9, or NP10; alternatively, NP11, NP13,or NP15; alternatively, NP16, NP18, or NP20; alternatively, StructureNP1; alternatively, Structure NP2; alternatively, Structure NP3;alternatively, Structure NP4; alternatively, Structure NP5;alternatively, NP6; alternatively, NP7; alternatively, NP8;alternatively, NP9; alternatively, NP10; alternatively, Structure NP11;alternatively, Structure NP13; alternatively, Structure NP15;alternatively, NP16; alternatively, NP 18; or alternatively, NP20.

In an embodiment, the N²-phosphinyl amidine compound comprising only oneN²-phosphinyl amidine group can be characterized by having the StructureNP1, NP6, NP11, or NP16; alternatively, Structure NP1 or NP6;alternatively, Structure NP11 or NP16; alternatively, Structure NP1 orNP11; or alternatively, Structure NP6 or NP16. In an embodiment, theN²-phosphinyl amidine compound comprising only two N²-phosphinyl amidinegroups can be characterized by having Structure NP2, NP3, NP8, NP13, orNP18; alternatively, Structure NP2, NP3, or NP8; alternatively,Structure NP13, or NP18; alternatively, Structure NP2 or NP3;alternatively, Structure NP3 or NP13; or alternatively, Structure NP8 orNP18. In other embodiments, N²-phosphinyl amidine compounds having atleast one N²-phosphinyl amidine group can be characterized by having theStructure NP4 NP5, NP9, NP10, NP15, or NP20; alternatively, StructureNP4, NP5, NP9, or NP10; alternatively, Structure NP15, or NP20;alternatively, Structure NP4 or NP5; alternatively, Structure NP9 orNP10; alternatively, Structure NP5 or NP15; or alternatively, StructureNP10 or NP20. R¹, R², R³, R⁴, R⁵, D¹, D², L¹, L², L³, Q¹, q, and rwithin N²-phosphinyl amidine compound Structures NP1—NP10, NP11, NP13,NP15, NP16, NP18, and/or NP20 are independently described herein and canbe utilized without limitation further describe the N²-phosphinylamidine compounds having Structures NP1-NP10, NP11, NP13, NP15, NP16,NP18, and/or NP20. In other embodiments, the N²-phosphinyl amidinecompounds can have any specific structure disclosed herein.

Generally, R¹ can be an organyl group; alternatively, an organyl groupconsisting essentially of inert functional groups; or alternatively, ahydrocarbyl group. In an embodiment, R¹ can be a C₁ to C₃₀ organylgroup; alternatively, a C₁ to C₂₀ organyl group; alternatively, a C₁ toC₁₅ organyl group; alternatively, a C₁ to C₁₀ organyl group; oralternatively, a C₁ to C₅ organyl group. In an embodiment, R¹ can be aC₁ to C₃₀ organyl group consisting essentially of inert functionalgroups; alternatively, a C₁ to C₂₀ organyl group consisting essentiallyof inert functional groups; alternatively, a C₁ to C₁₅ organyl groupconsisting essentially of inert functional groups; alternatively, a C₁to C₁₀ organyl group consisting essentially of inert functional groups;or alternatively, a C₁ to C₅ organyl group consisting essentially ofinert functional groups. In an embodiment, R¹ can be a C₁ to C₃₀hydrocarbyl group; alternatively, a C₁ to C₂₀ hydrocarbyl group;alternatively, a C₁ to C₁₅ hydrocarbyl group; alternatively, a C₁ to C₁₀hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarbyl group. Inyet other embodiments, R¹ can be a C₃ to C₃₀ aromatic group;alternatively, a C₃ to C₂₀ aromatic group; alternatively, a C₃ to C₁₅aromatic group; or alternatively, a C₃ to C₁₀ aromatic group.

In an aspect, R¹ can be a C₁ to C₃₀ alkyl group, a C₄ to C₃₀ cycloalkylgroup, a C₄ to C₃₀ substituted cycloalkyl group, a C₃ to C₃₀ aliphaticheterocyclic group, a C₃ to C₃₀ substituted aliphatic heterocyclicgroup, a C₆ to C₃₀ aryl group, a C₆ to C₃₀ substituted aryl group, a C₃to C₃₀ heteroaryl group, or a C₃ to C₃₀ substituted heteroaryl group;alternatively, a C₁ to C₃₀ alkyl group, a C₄ to C₃₀ cycloalkyl group, aC₄ to C₃₀ substituted cycloalkyl group, a C₆ to C₃₀ aryl group, or a C₆to C₃₀ substituted aryl group; alternatively, a C₄ to C₃₀ cycloalkylgroup or a C₄ to C₃₀ substituted cycloalkyl group; alternatively, a C₃to C₃₀ aliphatic heterocyclic group or a C₃ to C₃₀ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₃₀ aryl group or a C₆ to C₃₀substituted aryl group; alternatively, a C₃ to C₃₀ heteroaryl group or aC₃ to C₃₀ substituted heteroaryl group; alternatively, a C₁ to C₃₀ alkylgroup; alternatively, a C₄ to C₃₀ cycloalkyl group; alternatively, a C₄to C₃₀ substituted cycloalkyl group; alternatively, a C₃ to C₃₀aliphatic heterocyclic group; alternatively, a C₃ to C₃₀ substitutedaliphatic heterocyclic group; alternatively, a C₆ to C₃₀ aryl group;alternatively, a C₆ to C₃₀ substituted aryl group; alternatively, a C₃to C₃₀ heteroaryl group; or alternatively, a C₃ to C₃₀ substitutedheteroaryl group. In an embodiment, R¹ can be a C₁ to C₁₅ alkyl group, aC₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, aC₃ to C₂₀ aliphatic heterocyclic group, a C₃ to C₂₀ substitutedaliphatic heterocyclic group, a C₆ to C₂₀ aryl group, a C₆ to C₂₀substituted aryl group, a C₃ to C₂₀ heteroaryl group, or a C₃ to C₂₀substituted heteroaryl group; alternatively, a C₁ to C₁₅ alkyl group, aC₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, aC₆ to C₂₀ aryl group, or a C₆ to C₂₀ substituted aryl group;alternatively, a C₄ to C₂₀ cycloalkyl group or a C₄ to C₂₀ substitutedcycloalkyl group; alternatively, a C₃ to C₂₀ aliphatic heterocyclicgroup or a C₃ to C₂₀ substituted aliphatic heterocyclic group;alternatively, a C₆ to C₂₀ aryl group or a C₆ to C₂₀ substituted arylgroup; alternatively, a C₃ to C₂₀ heteroaryl group or a C₃ to C₂₀substituted heteroaryl group; alternatively, a C₁ to C₁₅ alkyl group;alternatively, a C₄ to C₂₀ cycloalkyl group; alternatively, a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₃ to C₂₀ aliphaticheterocyclic group; alternatively, a C₃ to C₂₀ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₂₀ aryl group;alternatively, a C₆ to C₂₀ substituted aryl group; alternatively, a C₃to C₂₀ heteroaryl group; or alternatively, a C₃ to C₂₀ substitutedheteroaryl group. In other embodiments, R¹ can be a C₁ to C₁₀ alkylgroup, a C₄ to C₁₅ cycloalkyl group, a C₄ to C₁₅ substituted cycloalkylgroup, a C₃ to C₁₅ aliphatic heterocyclic group, a C₃ to C₁₅ substitutedaliphatic heterocyclic group, a C₆ to C₁₅ aryl group, a C₆ to C₁₅substituted aryl group, a C₃ to C₁₅ heteroaryl group, or a C₃ to C₁₅substituted heteroaryl group; alternatively, a C₁ to C₁₀ alkyl group, aC₄ to C₁₅ cycloalkyl group, a C₄ to C₁₅ substituted cycloalkyl group, aC₆ to C₁₅ aryl group, or a C₆ to C₁₅ substituted aryl group;alternatively, a C₄ to C₁₅ cycloalkyl group or a C₄ to C₁₅ substitutedcycloalkyl group; alternatively, a C₃ to C₁₅ aliphatic heterocyclicgroup or a C₃ to C₁₅ substituted aliphatic heterocyclic group;alternatively, a C₆ to C₁₅ aryl group or a C₆ to C₁₅ substituted arylgroup; alternatively, a C₃ to C₁₅ heteroaryl group or a C₃ to C₁₅substituted heteroaryl group; alternatively, a C₁ to C₁₀ alkyl group;alternatively, a C₄ to C₁₅ cycloalkyl group; alternatively, a C₄ to C₁₅substituted cycloalkyl group; alternatively, a C₃ to C₁₅ aliphaticheterocyclic group; alternatively, a C₃ to C₁₅ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₁₅ aryl group;alternatively, a C₆ to C₁₅ substituted aryl group; alternatively, a C₃to C₁₅ heteroaryl group; or alternatively, a C₃ to C₁₅ substitutedheteroaryl group. In further embodiments, R¹ can be a C₁ to C₅ alkylgroup.

In an embodiment, R¹ can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, a undecyl group, a dodecylgroup, a tridecyl group, a tetradecyl group, a pentadecyl group, ahexadecyl group, a heptadecyl group, an octadecyl group, or a nonadecylgroup; or alternatively, a methyl group, an ethyl group, a propyl group,a butyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, or a decyl group. In some embodiments, R¹ can be amethyl group, an ethyl group, an n-propyl group, an iso-propyl group, ann-butyl group, an iso-butyl group, a sec-butyl group, a tert-butylgroup, an n-pentyl group, an iso-pentyl group, a sec-pentyl group, or aneopentyl group; alternatively, a methyl group, an ethyl group, aniso-propyl group, a tert-butyl group, or a neopentyl group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, an n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.In some embodiments, the alkyl groups which can be utilized as R¹ can besubstituted. Each substituent of a substituted alkyl group independentlycan be a halogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Halogens and hydrocarboxy groupsthat can be utilized as substituents are independently disclosed hereinand can be utilized without limitation to further describe thesubstituted alkyl group which can be utilized as R¹.

In an embodiment, R¹ can be a cyclobutyl group, a substituted cyclobutylgroup, a cyclopentyl group, a substituted cyclopentyl group, acyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, asubstituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. In some embodiments, R¹ can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. In other embodiments, R¹ can be a cyclobutyl group ora substituted cyclobutyl group; alternatively, a cyclopentyl group or asubstituted cyclopentyl group; alternatively, a cyclohexyl group or asubstituted cyclohexyl group; alternatively, a cycloheptyl group or asubstituted cycloheptyl group; or alternatively, a cyclooctyl group or asubstituted cyclooctyl group. In further embodiments, R¹ can be acyclopentyl group; alternatively, a substituted cyclopentyl group; acyclohexyl group; or alternatively, a substituted cyclohexyl group.Substituents for the substituted cycloalkyl group are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the substituted cycloalkyl group which can be utilized as R¹.

In an embodiment, each substituent for a substituted cycloalkyl group(general or specific) that can be utilized as R¹ independently can be ahalogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, ahalogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituent for a substituted cycloalkyl group (general or specific)that can be utilized as R¹ independently can be a halogen, an alkylgroup, or an alkoxy group; alternatively, a halogen or an alkyl group;alternatively, a halogen or an alkoxy group; alternatively, an alkylgroup or an alkoxy group; alternatively, a halogen; alternatively, analkyl group; or alternatively, an alkoxy group. Specific substituenthalogens, hydrocarbyl groups, hydrocarboxy groups, alkyl group, andalkoxy groups are independently disclosed herein and can be utilizedwithout limitation to further describe the substituents for asubstituted cycloalkyl group (general or specific) that can be utilizedas R¹.

In an aspect, R¹ can have Structure G1:

wherein the undesignated valency is attached to the N¹ nitrogen atom ofthe N²-phosphinyl amidine group. Generally, R^(11c), R^(12c), R^(13c),R^(14c), and R^(15c) can independently be hydrogen or a non-hydrogensubstituent, and n can be an integer from 1 to 5. In an embodimentwherein R¹ has Structure G1, R^(11c), R^(13c), R^(14c), and R^(15c) canbe hydrogen and R^(12c) can be any non-hydrogen substituent disclosedherein; or alternatively, R^(11c), R^(13c), and R^(15c) can be hydrogenand R^(12c) and R^(14c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively, 3. Substituents for the R¹group having Structure G1 are independently disclosed herein and can beutilized without limitation to further describe the R¹ group havingStructure G1.

In an embodiment, R^(11c), R^(12c), R^(13c), R^(14c), and R^(15c)independently can be hydrogen, a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, hydrogen, a halogen, or a hydrocarbylgroup; alternatively, hydrogen, a halogen, or a hydrocarboxy group;alternatively, hydrogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, hydrogen or a halogen; alternatively, hydrogen or ahydrocarbyl group; or alternatively, hydrogen or a hydrocarboxy group.In some embodiments, R^(11c), R^(12c), R^(13c), R^(14c), and R^(15c)independently can be hydrogen, a halogen, and alkyl group, or an alkoxygroup; alternatively, hydrogen, a halogen, or an alkyl group;alternatively, hydrogen, a halogen, and an alkoxy group; alternatively,hydrogen or a halogen; alternatively, hydrogen or an alkyl group; oralternatively, hydrogen or an alkoxy group. Specific substituenthalogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups, andalkoxy groups are independently disclosed herein and can be utilizedwithout limitation to further describe the R¹ group having Structure G1.

In an embodiment wherein R¹ has Structure G1, R^(11c), R^(13c), R^(14c),and R^(15c) can be hydrogen and R^(12c) can be any non-hydrogensubstituent indicated herein; or alternatively, R^(11c), R^(13c), andR^(15c) can be hydrogen and R^(12c) and R^(14c) can be any non-hydrogensubstituent indicated herein. In some embodiments, wherein R¹ hasStructure G1, R^(11c), R^(13c), R^(14c), and R^(15c) can be hydrogen andR^(12c) can be any alkyl group, alkoxy group, or halogen indicatedherein; or alternatively, R^(11c), R^(13c), and R^(15c) can be hydrogenand R^(12c) and R^(14c) can be any alkyl group, alkoxy group, or halogenindicated herein. In other embodiments, wherein R¹ has Structure G1,R^(11c), R^(13c), R^(14c), and R^(15c) can be hydrogen and R^(12c) canbe any alkyl group substituent indicated herein; or alternatively,R^(11c), R^(13c), and R^(15c) can be hydrogen and R^(12c) and R^(14c)can be any alkyl group substituent indicated herein. In anotherembodiment wherein R¹ has Structure G1, R^(11c), R^(12c), R^(13c),R^(14c), and R^(15c) can be hydrogen. In an embodiment, R^(11c),R^(12c), R^(13c), R^(14c), and R^(15c) independently can be hydrogen, oran alkyl group; alternatively, R^(11c), R^(12c), and R^(14c) can behydrogen and R^(13c) and R^(15c) can be are alkyl groups; oralternatively, R^(11c) can be hydrogen and R^(12c), R^(13c), R^(14c),and R^(15c) can be alkyl groups. Specific substituent halogens,hydrocarbyl groups, hydrocarboxy groups, alkyl group, and alkoxy groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the R¹ group having Structure G1.

In an aspect, R¹ can be a phenyl group, a substituted phenyl group, anaphthyl group, or a substituted naphthyl group. In an embodiment, R¹can be a phenyl group or a substituted phenyl group; alternatively, anaphthyl group or a substituted naphthyl group; alternatively, a phenylgroup or a naphthyl group; or alternatively, a substituted phenyl groupor a substituted naphthyl group. In some embodiments, R¹ can be a phenylgroup; alternatively, a substituted phenyl group; alternatively, anaphthyl group; or alternatively, a substituted naphthyl group.

In an embodiment, the R¹ substituted phenyl group can be a 2-substitutedphenyl group, a 3-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, a 2,6-disubstituted phenylgroup, 3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenylgroup. In other embodiments, the R¹ substituted phenyl group can be a2-substituted phenyl group, a 4-substituted phenyl group, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2-substituted phenylgroup, a 4-substituted phenyl group, a 2,4-disubstituted phenyl group,or a 2,6-disubstituted phenyl group; alternatively, a 3-substitutedphenyl group or a 3,5-disubstituted phenyl group; alternatively, a2-substituted phenyl group or a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group, a 2,6-disubstitutedphenyl group, or a 2,4,6-trisubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group or a 2,4,6-trisubstituted phenyl group;alternatively, a 2,4-disubstituted phenyl group or a 2,6-disubstitutedphenyl group; alternatively, a 2-substituted phenyl group;alternatively, a 3-substituted phenyl group; alternatively, a4-substituted phenyl group; alternatively, a 2,4-disubstituted phenylgroup; alternatively, a 2,6-disubstituted phenyl group; alternatively, a3,5-disubstituted phenyl group; or alternatively, a 2,4,6-trisubstitutedphenyl group.

In an embodiment, R¹ can be a naphth-1-yl group, a substitutednaphth-1-yl group, a naphth-2-yl group, or a substituted naphth-2-ylgroup. In some embodiments, R¹ can be a naphth-1-yl group or asubstituted naphth-1-yl group; alternatively, a naphth-2-yl group or asubstituted naphth-2-yl group; alternatively, a naphth-1-yl group;alternatively, a substituted naphth-1-yl group; alternatively, anaphth-2-yl group; or alternatively, a substituted naphth-2-yl group. Inother embodiments, R¹ can be a 2-substituted naphth-1-yl group, a3-substituted naphth-1-yl group, a 4-substituted naphth-1-yl group, or a8-substituted naphth-1-yl group; alternatively, a 2-substitutednaphth-1-yl group; alternatively, a 3-substituted naphth-1-yl group;alternatively, a 4-substituted naphth-1-yl group; or alternatively, a8-substituted naphth-1-yl group. In further embodiments, R¹ can be a1-substituted naphth-2-yl group, a 3-substituted naphth-2-yl group, a4-substituted naphth-2-yl group, or a 1,3-disubstituted naphth-2-ylgroup; alternatively, a 1-substituted naphth-2-yl group; alternatively,a 3-substituted naphth-2-yl group; alternatively, a 4-substitutednaphth-2-yl group; or alternatively, a 1,3-disubstituted naphth-2-ylgroup. Substituents for the substituted phenyl or substituted naphthylgroup that can be utilized as R¹ are independently disclosed herein.These substituents can be utilized without limitation to furtherdescribe the substituted phenyl groups or substituted naphthyl groupswhich can be utilized as R¹.

In an embodiment, each substituent for a substituted phenyl orsubstituted naphthyl R¹ group independently can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituents for the substituted phenyl or substituted naphthyl R¹ groupindependently can be a halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, a halogen oran alkoxy group; alternatively, an alkyl group or an alkoxy group;alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Specific substituent halogens,hydrocarbyl groups, hydrocarboxy groups, alkyl groups, and alkoxy groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents for the substitutedphenyl or substituted naphthyl R¹ group.

In an aspect, the R¹ can have Structure G2:

wherein the undesignated valency is attached to the N¹ nitrogen atom ofthe N²-phosphinylamidine group. Generally, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶independently can be hydrogen or a non-hydrogen substituent. In anembodiment wherein R¹ has Structure G2, R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ canbe hydrogen, R¹³, R¹⁴, R¹⁵, and R¹⁶ can be hydrogen and R¹² can be anon-hydrogen substituent, R¹², R¹⁴, R¹⁵, and R¹⁶ can be hydrogen and R¹³can be a non-hydrogen substituent, R¹², R¹³, R¹⁵, and R¹⁶ can behydrogen and R¹⁴ can be a non-hydrogen substituent, R¹³, R¹⁵, and R¹⁶can be hydrogen and R¹² and R¹⁴ can be non-hydrogen substituents, R¹³,R¹⁴, and R¹⁵ can be hydrogen and R¹² and R¹⁶ can be non-hydrogensubstituents, R¹², R¹⁴, and R¹⁶ can be hydrogen and R¹³ and R¹⁵ can benon-hydrogen substituents, or R¹³ and R¹⁵ can be hydrogen and R¹², R¹⁴,and R¹⁶ can be non-hydrogen substituents. In some embodiments wherein R¹has Structure G2, R¹³, R¹⁴, R¹⁵, and R¹⁶ can be hydrogen and R¹² can bea non-hydrogen substituent, R¹², R¹³, R¹⁵, and R¹⁶ can be hydrogen andR¹⁴ can be a non-hydrogen substituent, R¹³, R¹⁵, and R¹⁶ can be hydrogenand R¹² and R¹⁴ can be non-hydrogen substituents, R¹³, R¹⁴, and R¹⁵ canbe hydrogen and R¹² and R¹⁶ can be non-hydrogen substituents, or R¹³ andR¹⁵ can be hydrogen and R¹², R¹⁴, and R¹⁶ can be non-hydrogensubstituents; alternatively, R¹³, R¹⁴, R¹⁵, and R¹⁶ can be hydrogen andR¹² can be a non-hydrogen substituent, R¹², R¹³, R¹⁵, and R¹⁶ can behydrogen and R¹⁴ can be a non-hydrogen substituent, R¹³, R¹⁵, and R¹⁶can be hydrogen and R¹² and R¹⁴ can be non-hydrogen substituents, orR¹³, R¹⁴, and R¹⁵ can be hydrogen and R¹² and R¹⁶ can be non-hydrogensubstituents; alternatively, R¹², R¹⁴, R¹⁵, and R¹⁶ can be hydrogen andR¹³ can be a non-hydrogen substituent, or R¹², R¹⁴, R¹⁵, and R¹⁶ can behydrogen and R¹³ and R¹⁵ can be non-hydrogen substituents;alternatively, R¹³, R¹⁴, and R¹⁶ can be hydrogen and R¹² can be anon-hydrogen substituent, or R¹², R¹³, R¹⁴, and R¹⁶ can be hydrogen andR¹⁴ can be a non-hydrogen substituent; alternatively, R¹³, R¹⁵, and R¹⁶can be hydrogen and R¹² and R¹⁴ can be non-hydrogen substituents, R¹³,R¹⁴, and R¹⁵ can be hydrogen and R¹² and R¹⁶ can be non-hydrogensubstituents, or R¹³ and R¹⁵ can be hydrogen and R¹², R¹⁴ and R¹⁶ can benon-hydrogen substituents; or alternatively, R¹³, R¹⁵, and R¹⁶ can behydrogen and R¹² and R¹⁴ can be non-hydrogen substituents, or R¹³, R¹⁴,and R¹⁵ can be hydrogen and R¹² and R¹⁶ can be non-hydrogensubstituents. In other embodiments wherein R¹ has Structure G2, R¹²,R¹³, R¹⁴, R¹⁵, and R¹⁶ can be hydrogen; alternatively, R¹³R¹⁴, R¹⁵, andR¹⁶ can be hydrogen and R¹² can be a non-hydrogen substituent;alternatively, R¹², R¹⁴, R¹⁵, and R¹⁶ can be hydrogen and R¹³ can be anon-hydrogen substituent; alternatively, R¹², R¹³, R¹⁵, and R¹⁶ can behydrogen and R¹⁴ can be a non-hydrogen substituent; alternatively, R¹³,R¹⁵, and R¹⁶ can be hydrogen and R¹² and R¹⁴ can be non-hydrogensubstituents; alternatively, R¹³, R¹⁴, and R¹⁵ can be hydrogen and R¹²and R¹⁶ can be non-hydrogen substituents; alternatively, R¹², R¹⁴, andR¹⁶ can be hydrogen and R¹³ and R¹⁵ and can be non-hydrogensubstituents; or alternatively, R¹³ and R¹⁵ can be hydrogen and R¹²,R¹⁴, and R¹⁶ can be non-hydrogen substituents. Substituents for the R¹group having Structure G2 are independently disclosed herein and can beutilized without limitation to further describe the R¹ group havingStructure G2.

In an embodiment, the non-hydrogen substituents that can be utilized asR¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ in the R¹ group having Structure G2independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, the non-hydrogen substituents that can be utilized as R¹²,R¹³, R¹⁴, R¹⁵, and R¹⁶ in the R¹ group having Structure G2 independentlycan be a halogen, an alkyl group, and an alkoxy group; alternatively, ahalogen or an alkyl group; alternatively, a halogen or an alkoxy group;alternatively, an alkyl group or an alkoxy group; alternatively, ahalogen; alternatively, an alkyl group; or alternatively, an alkoxygroup. Specific substituent halogens, hydrocarbyl groups, hydrocarboxygroups, alkyl group, and alkoxy groups are independently disclosedherein and can be utilized without limitation to further describe the R¹group having Structure G2.

In an aspect, R¹ can be a pyridinyl group, a substituted pyridinylgroup, a furyl group, a substituted furyl group, a thienyl group, or asubstituted thienyl group. In an embodiment, R¹ can be a pyridinyl groupor a substituted pyridinyl group; alternatively, a furyl group or asubstituted furyl group; or alternatively, a thienyl group or asubstituted thienyl group. In some embodiments, R¹ can be a pyridinylgroup, a furyl group, or a thienyl group. In other embodiments, R¹ canbe a pyridinyl group; alternatively, a substituted pyridinyl group;alternatively, a furyl group; alternatively, a substituted furyl group;alternatively, a thienyl group; or alternatively, a substituted thienylgroup.

In an embodiment, the pyridinyl (or substituted pyridinyl) R¹ group canbe a pyridin-2-yl group, a substituted pyridin-2-yl group, apyridin-3-yl group, a substituted pyridin-3-yl group, a pyridin-4-ylgroup, or a substituted pyridin-4-yl group; alternatively, apyridin-2-yl group, a pyridin-3-yl group, or a pyridin-4-yl group. Insome embodiments, the pyridinyl (or substituted pyridinyl) R¹ group canbe a pyridin-2-yl group or a substituted pyridin-2-yl group;alternatively, a pyridin-3-yl group or a substituted pyridin-3-yl group;alternatively, a pyridin-4-yl group or a substituted pyridin-4-yl group;alternatively, a pyridin-2-yl group; alternatively, a substitutedpyridin-2-yl group; alternatively, a pyridin-3-yl group; alternatively,a substituted pyridin-3-yl group; alternatively, a pyridin-4-yl group;or alternatively, a substituted pyridin-4-yl group. In an embodiment,the substituted pyridinyl R¹ group can be a 2-substituted pyridin-3-ylgroup, a 4-substituted pyridin-3-yl group, a 5-substituted pyridin-3-ylgroup, a 6-substituted pyridin-3-yl group, a 2,4-disubstitutedpyridin-3-yl group, a 2,6-disubstituted pyridin-3-yl group, or a2,4,6-trisubstituted pyridin-3-yl group; alternatively, 2-substitutedpyridin-3-yl group, a 4-substituted pyridin-3-yl group, or a6-substituted pyridin-3-yl group; alternatively, a 2,4-disubstitutedpyridin-3-yl group or a 2,6-disubstituted pyridin-3-yl group;alternatively, a 2-substituted pyridin-3-yl group; alternatively, a4-substituted pyridin-3-yl group; alternatively, a 5-substitutedpyridin-3-yl group; alternatively, a 6-substituted pyridin-3-yl group;alternatively, a 2,4-disubstituted pyridin-3-yl group; alternatively, a2,6-disubstituted pyridin-3-yl group; or alternatively, a2,4,6-trisubstituted pyridin-3-yl group. In an embodiment, thesubstituted pyridinyl R¹ group can be a 2-substituted pyridin-4-ylgroup, a 3-substituted pyridin-4-yl group, a 5-substituted pyridin-4-ylgroup, a 6-substituted pyridin-4-yl group, a 2,6-disubstitutedpyridin-4-yl group, or a 3,5-disubstituted pyridin-4-yl group;alternatively, a 2-substituted pyridin-4-yl group or a 6-substitutedpyridin-4-yl group; alternatively, a 3-substituted pyridin-4-yl group ora 5-substituted pyridin-4-yl group; alternatively, a 2-substitutedpyridin-4-yl group; alternatively, a 3-substituted pyridin-4-yl group;alternatively, a 5-substituted pyridin-4-yl group; alternatively, a6-substituted pyridin-4-yl group; alternatively, a 2,6-disubstitutedpyridin-4-yl group; or alternatively, a 3,5-disubstituted pyridin-4-ylgroup. Substituents for the substituted pyridinyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted pyridinyl groups which can be utilizedas R¹.

In an embodiment, the furyl (or substituted furyl) R¹ group can be afur-2-yl group, a substituted fur-2-yl group, a fur-3-yl group, or asubstituted fur-3-yl group; alternatively, a fur-2-yl or a fur-3-ylgroup. In some embodiments, the furyl (or substituted furyl) R¹ groupcan be a fur-2-yl group or a substituted fur-2-yl group; alternatively,a fur-3-yl group or a substituted fur-3-yl group; alternatively, afur-2-yl group; alternatively, a substituted fur-2-yl group;alternatively, a fur-3-yl group; or alternatively, a substitutedfur-3-yl group. In an embodiment, the substituted furyl R¹ group can bea 2-substituted fur-3-yl group, a 4-substituted fur-3-yl group, or a2,4-disubstituted fur-3-yl group; alternatively, a 2-substitutedfur-3-yl group; alternatively, a 4-substituted fur-3-yl group; oralternatively, a 2,4-disubstituted fur-3-yl group. Substituents for thesubstituted furyl groups are independently disclosed herein and can beutilized without limitation to further describe the substituted furylgroups which can be utilized as R¹.

In an embodiment, a thienyl (or substituted thienyl) R¹ group be athien-2-yl group, a substituted thien-2-yl group, a thien-3-yl group, ora substituted thien-3-yl group; alternatively, a thien-2-yl group or athien-3-yl group. In some embodiments, the thienyl (or substitutedthienyl) R¹ group can be a thien-2-yl group or a substituted thien-2-ylgroup; alternatively, a thien-3-yl group or a substituted thien-3-ylgroup; alternatively, a thien-2-yl group; alternatively, a substitutedthien-2-yl group; alternatively, a thien-3-yl group; or alternatively, asubstituted thien-3-yl group. In an embodiment, the substituted thienylR¹ group can be a 2-substituted thien-3-yl group, a 4-substitutedthien-3-yl group, or a 2,4-disubstituted thien-3-yl group;alternatively, a 2-substituted thien-3-yl group; alternatively, a4-substituted thien-3-yl group; or alternatively, a 2,4-disubstitutedthien-3-yl group. Substituents for the substituted thienyl groups areindependently disclosed herein and can be utilized without limitation tofurther describe the substituted thienyl groups which can be utilized asR¹.

In an aspect, R¹ can be a C₁ to C₃₀ organoheteryl group; alternatively,a C₁ to C₂₀ organoheteryl group; alternatively, a C₁ to C₁₅organoheteryl group; alternatively, a C₁ to C₁₀ organoheteryl group; oralternatively, a C₁ to C₅ organoheteryl group. In an embodiment, R¹ canbe a C₄ to C₃₀ cycloheteryl group; alternatively, a C₄ to C₂₀cycloheteryl group; alternatively, a C₄ to C₁₅ cycloheteryl group; oralternatively, a C₄ to C₁₀ cycloheteryl group. In some embodiments, thecycloheteryl group which can be utilized as R¹ can be a substitutedcycloheteryl group.

In some embodiments, R¹ can be a C₁ to C₃₀ hydrocarbyl aminyl group, aC₂ to C₃₀ dihydrocarbyl aminyl group, a C₄ to C₃₀ cycloaminyl group, ora C₄ to C₃₀ substituted cycloaminyl group; alternatively, a C₁ to C₃₀hydrocarbyl aminyl group or a C₂ to C₃₀ dihydrocarbyl aminyl group;alternatively, a C₄ to C₃₀ cycloaminyl group or a C₄ to C₃₀ substitutedcycloaminyl group; alternatively, a C₂ to C₃₀ dihydrocarbyl aminyl groupor a C₄ to C₃₀ cycloaminyl group; alternatively, a C₁ to C₃₀ hydrocarbylaminyl group; alternatively, a C₂ to C₃₀ dihydrocarbyl aminyl group;alternatively, a C₄ to C₃₀ cycloaminyl group; or alternatively, a C₄ toC₃₀ substituted cycloaminyl group. In other embodiments, R¹ can be a C₁to C₂₀ hydrocarbyl aminyl group, a C₂ to C₂₀ dihydrocarbyl aminyl group,a C₄ to C₂₀ cycloaminyl group, or a C₄ to C₂₀ substituted cycloaminylgroup; alternatively, a C₁ to C₂₀ hydrocarbyl aminyl group or a C₂ toC₂₀ dihydrocarbyl aminyl group; alternatively, a C₄ to C₂₀ cycloaminylgroup or a C₄ to C₂₀ substituted cycloaminyl group; alternatively, a C₂to C₂₀ dihydrocarbyl aminyl group or a C₄ to C₂₀ cycloaminyl group;alternatively, a C₁ to C₂₀ hydrocarbyl aminyl group; alternatively, a C₂to C₂₀ dihydrocarbyl aminyl group; alternatively, a C₄ to C₂₀cycloaminyl group; or alternatively, a C₄ to C₂₀ substituted cycloaminylgroup. In yet other embodiments, R¹ can be a C₁ to C₁₀ hydrocarbylaminyl group, a C₂ to C₁₅ dihydrocarbyl aminyl group, a C₄ to C₁₅cycloaminyl group, or a C₄ to C₁₅ substituted cycloaminyl group;alternatively, a C₁ to C₁₀ hydrocarbyl aminyl group or a C₂ to C₁₅dihydrocarbyl aminyl group; alternatively, a C₄ to C₁₅ cycloaminyl groupor a C₄ to C₁₅ substituted cycloaminyl group; alternatively, a C₂ to C₁₅dihydrocarbyl aminyl group or a C₄ to C₁₅ cycloaminyl group;alternatively, a C₁ to C₁₀ hydrocarbyl aminyl group; alternatively, a C₂to C₁₅ dihydrocarbyl aminyl group; alternatively, a C₄ to C₁₅cycloaminyl group; or alternatively, a C₄ to C₁₅ substituted cycloaminylgroup. In further embodiments, R¹ can be a C₁ to C₅ hydrocarbyl aminylgroup, a C₂ to C₁₀ dihydrocarbyl aminyl group, a C₄ to C₁₀ cycloaminylgroup, or a C₄ to C₁₀ substituted cycloaminyl group; alternatively, a C₁to C₅ hydrocarbyl aminyl group or a C₂ to C₁₀ dihydrocarbyl aminylgroup; alternatively, a C₄ to C₁₀ cycloaminyl group or a C₄ to C₁₀substituted cycloaminyl group; alternatively, a C₂ to C₁₀ dihydrocarbylaminyl group or a C₄ to C₁₀ cycloaminyl group; alternatively, a C₁ to C₅hydrocarbyl aminyl group; alternatively, a C₂ to C₁₀ dihydrocarbylaminyl group; alternatively, a C₄ to C₁₀ cycloaminyl group; oralternatively, a C₄ to C₁₀ substituted cycloaminyl group.

In an embodiment, each hydrocarbyl group of a hydrocarbyl aminyl groupor a dihydrocarbyl aminyl group can be a C₁ to C₃₀ hydrocarbyl group;alternatively, a C₁ to C₂₀ hydrocarbyl group; alternatively, a C₁ to C₁₅hydrocarbyl group; alternatively, a C₁ to C₁₀ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group. In an embodiment, eachhydrocarbyl group of a hydrocarbyl aminyl group or a dihydrocarbylaminyl group can be an alkyl group, a cycloalkyl group, an aryl group,or an aralkyl group; alternatively, an alkyl group; alternatively, acycloalkyl group; alternatively, an aryl group; or alternatively, oraralkyl group. Alkyl groups, cycloalkyl groups, aryl group, and aralkylgroups have been described herein a potential R¹, R², R³, R⁴, and R⁵groups (among other potential group) and these alkyl groups, cycloalkylgroups, aryl group, and aralkyl groups can be utilized withoutlimitation to further describe the hydrocarbyl aminyl group and/or adihydrocarbyl aminyl group that can be utilized a R¹.

In an embodiment, R¹ can be a pyrrolidin-1-yl group, a substitutedpyrrolidin-1-yl group, a piperidin-1-yl group, a substitutedpiperidin-1-yl group, a morphilin-1-yl group, a susbstitutedmorphilin-1-yl group, a pyrrol-1-yl group, or a substituted pyrrol-ylgroup. In some embodiments, R¹ can be a pyrrolidin-1-yl group, asubstituted pyrrolidin-1-yl group, a piperidin-1-yl group, or asubstituted piperidin-1-yl group; a pyrrolidin-1-yl group or asubstituted pyrrolidin-1-yl group; alternatively, a piperidin-1-yl groupor a substituted piperidin-1-yl group; alternatively, a morphilin-1-ylgroup or a substituted morphilin-1-yl group; alternatively, apyrrol-1-yl group or a substituted pyrrol-yl group; alternatively, apyrrolidin-1-yl group, a piperidin-1-yl group, a morphilin-1-yl group,or a pyrrol-1-yl group; alternatively, a pyrrolidin-1-yl group or apiperidin-1-yl group; alternatively, a pyrrolidin-1-yl group;alternatively, a substituted pyrrolidin-1-yl group; alternatively, apiperidin-1-yl group; alternatively, a substituted piperidin-1-yl group;alternatively, a morphilin-1-yl group; alternatively, a substitutedmorphilin-1-yl group; alternatively, a pyrrol-1-yl group; oralternatively, a substituted pyrrol-yl group. Generally, these specificcycloaminyl groups can have the same number of carbon atoms as thecycloaminyl and substituted cycloaminyl group described herein.Substituents for the substituted cycloaminyl group (general or specific)that can be utilized as R¹ are independently disclosed herein. Thesesubstituents can be utilized without limitation to further describe thesubstituted cycloaminyl groups (general or specific) which can beutilized as R¹.

In an embodiment, each substituent for a substituted pyridinyl, furyl,and/or thienyl group (general or specific) that can be utilized as R¹independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, each substituent for a substituted pyridinyl, furyl, and/orthienyl group (general or specific) that can be utilized as R¹independently can be a halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, a halogen oran alkoxy group; alternatively, an alkyl group or an alkoxy group;alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Specific substituent halogens,hydrocarbyl groups, hydrocarboxy groups, alkyl group, and alkoxy groupsare independently disclosed herein and can be utilized withoutlimitation to further describe the substituents for the substitutedpyridinyl, furyl, and/or thienyl groups (general or specific) that canbe utilized as R¹.

In an aspect, when the N¹ nitrogen atom of the N²-phosphinyl amidinegroup is attached to an atom (carbon or a heteroatom) of a ring or ringsystem group (cycloalkane group, aliphatic heterocyclic group,cyclohetero group, aromatic group, arene group, heteroarene group,arylhetero group, or any other disclosed herein), the cyclic R¹ groupcan comprise at least one substituent at an atom adjacent to the atomattached to N¹ nitrogen atom of the N²-phosphinyl amidine group. In anembodiment, when the N¹ nitrogen atom of the N²-phosphinyl amidine groupis attached to an atom (carbon or a heteroatom) of a ring or ring systemgroup (cycloalkane group, aliphatic heterocyclic group, cycloheterogroup, aromatic group, arene group, heteroarene group, or arylheterogroup, or any other disclosed herein) the cyclic R¹ group can compriseat least one substituent at each atom adjacent to the atom attached toN¹ nitrogen atom of the N²-phosphinyl amidine group. In anotherembodiment, when the N¹ nitrogen atom of the N²-phosphinyl amidine groupis attached to an atom (carbon or a heteroatom) of a ring or ring systemgroup (cycloalkane group, aliphatic heterocyclic group, cycloheterogroup, aromatic group, arene group, heteroarene group, or arylheterogroup, or any other disclosed herein), the cyclic R¹ group can consistof one substituent at each atom adjacent to the atom attached to N¹nitrogen atom of the N²-phosphinyl amidine group. In other embodiments,when the N¹ nitrogen atom of the N²-phosphinyl amidine group is attachedto an atom (carbon or a heteroatom) of a ring or ring system group(cycloalkane group, aliphatic heterocyclic group, cyclohetero group,aromatic group, arene group, heteroarene group, or arylhetero group, orany other disclosed herein), the cyclic R¹ group can comprise only onesubstituent at an atom adjacent to the atom attached to N¹ nitrogen atomof the N²-phosphinyl amidine group. In another embodiment, when the N¹nitrogen atom of the N²-phosphinyl amidine group is attached to an atom(carbon or a heteroatom) of a ring or ring system group (cycloalkanegroup, aliphatic heterocyclic group, cyclohetero group, aromatic group,arene group, heteroarene group, or arylhetero group, or any otherdisclosed herein), the cyclic R¹ group can comprise only one substituentat each atom adjacent to the atom attached to N¹ nitrogen atom of theN²-phosphinyl amidine group. In yet another embodiment, when the N¹nitrogen atom of the N²-phosphinyl amidine group is attached to an atom(carbon or a heteroatom) of a ring or ring system group (cycloalkanegroup, aliphatic heterocyclic group, cyclohetero group, aromatic group,arene group, heteroarene group, or arylhetero group, or any otherdisclosed herein), the cyclic R¹ group can consist of only onesubstituent located at each atom adjacent to the atom attached to N¹nitrogen atom of the N²-phosphinyl amidine group.

In an embodiment, when the N¹ nitrogen atom of the N²-phosphinyl amidinegroup is attached to a carbon atom of a cycloalkane or arene ring orring system, the cyclic R¹ group can comprise at least one substituentlocated on a carbon atom adjacent to the carbon atom attached to N¹nitrogen atom of the N²-phosphinyl amidine group. In some embodiments,when the N¹ nitrogen atom of the N²-phosphinyl amidine group is attachedto a carbon atom of a cycloalkane or arene ring or ring system, thecyclic R¹ group can comprise at least one substituent located on eachcarbon atom adjacent to the carbon atom attached to N¹ nitrogen atom ofthe N²-phosphinyl amidine group. In another embodiment, when the N¹nitrogen atom of the N²-phosphinyl amidine group is attached to a carbonatom of a cycloalkane or arene ring or ring system, the cyclic R¹ groupcan consist of one substituent located on each carbon atom adjacent tothe carbon atom attached to N¹ nitrogen atom of the N²-phosphinylamidine group. In other embodiments, when the N¹ nitrogen atom of theN²-phosphinyl amidine group is attached to a carbon atom of acycloalkane or arene ring or ring system, the cyclic R¹ group cancomprise only one substituent located on a carbon atom adjacent to thecarbon atom attached to N¹ nitrogen atom of the N²-phosphinyl amidinegroup. In another embodiment, when the N¹ nitrogen atom of theN²-phosphinyl amidine group is attached to a carbon atom of acycloalkane or arene ring or ring system, the cyclic R¹ group cancomprise only one substituent located on each carbon atom adjacent tothe carbon atom attached to N¹ nitrogen atom of the N²-phosphinylamidine group. In yet another embodiment, when the N¹ nitrogen atom ofthe N²-phosphinyl amidine group is attached to a carbon atom of acycloalkane or arene ring or ring system, the cyclic R¹ group canconsist of only one substituent located on each carbon atom adjacent tothe carbon atom attached to N¹ nitrogen atom of the N²-phosphinylamidine group.

The non-hydrogen substituents of any substituted R¹ group (general orspecific) independently can be a hydrocarbyl group or an inertfunctional group. Non-limiting examples of inert functional groupinclude halogens and hydrocarboxy groups. In an embodiment, eachnon-hydrogen substituent any substituted R¹ group (general or specific)independently can be a halide, a C₁ to C₁₀ hydrocarbyl group, or a C₁ toC₁₀ hydrocarboxy group; alternatively, a halide or a C₁ to C₁₀hydrocarbyl group; alternatively, a halide or a C₁ to C₁₀ hydrocarboxygroup; alternatively, a C₁ to C₁₀ hydrocarbyl group or a C₁ to C₁₀hydrocarboxy group; alternatively, a halide; alternatively, a C₁ to C₁₀hydrocarbyl group; or alternatively, a C₁ to C₁₀ hydrocarboxy group. Inother embodiments, each non-hydrogen substituent any substituted R¹group (general or specific) independently can be a halide, a C₁ to C₅hydrocarbyl group, or a C₁ to C₅ hydrocarboxy group; alternatively, ahalide or a C₁ to C₅ hydrocarbyl group; alternatively, a halide or a C₁to C₅ hydrocarboxy group; alternatively, a C₁ to C₅ hydrocarbyl group ora C₁ to C₅ hydrocarboxy group; alternatively, a halide; alternatively, aC₁ to C₅ hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarboxygroup.

In an embodiment, each halide substituent for any substituted R¹ group(general or specific) independently can be a fluoride, chloride,bromide, or iodide; alternatively, a fluoride or chloride. In someembodiments, each halide substituent any substituted R¹ group (generalor specific) independently can be a fluoride; alternatively, a chloride;alternatively, a bromide; or alternatively, an iodide.

In an embodiment, each hydrocarbyl substituent for any substituted R¹group (general or specific) independently can be an alkyl group, an arylgroup, or an aralkyl group; alternatively, an alkyl group;alternatively, an aryl group; or alternatively, an aralkyl group. In anembodiment, each alkyl substituent for any substituted R¹ group (generalor specific) independently can be a methyl group, an ethyl group, ann-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group,an isobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentylgroup, a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group,a 3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentylgroup; alternatively, a methyl group, an ethyl group, an isopropylgroup, a tert-butyl group, or a neo-pentyl group; alternatively, amethyl group; alternatively, an ethyl group; alternatively, an isopropylgroup; alternatively, a tert-butyl group; or alternatively, a neo-pentylgroup. In an embodiment, each aryl substituent for any substituted R¹group (general or specific) independently can be a phenyl group, a tolylgroup, a xylyl group, or a 2,4,6-trimethylphenyl group; alternatively, aphenyl group; alternatively, a tolyl group; alternatively, a xylylgroup; or alternatively, a 2,4,6-trimethylphenyl group. In anembodiment, each aralkyl substituent for any substituted R¹ group(general or specific) independently can be a benzyl group or anethylphenyl group (2-phenyleth-1-yl or 1-phenyleth-1-yl); alternatively,a benzyl group; alternatively, an ethylphenyl group; alternatively, a2-phenyleth-1-yl group; or alternatively, a 1-phenyleth-1-yl group.

In an embodiment, each hydrocarboxy substituent for any substituted R¹group (general or specific) independently can be an alkoxy group, anaryloxy group, or an aralkoxy group; alternatively, an alkoxy group;alternatively, an aryloxy group; or alternatively, an aralkoxy group. Inan embodiment, each alkoxy substituent for any substituted R¹ group(general or specific) independently can be a methoxy group, an ethoxygroup, an n-propoxy group, an isopropoxy group, an n-butoxy group, asec-butoxy group, an isobutoxy group, a tert-butoxy group, an n-pentoxygroup, a 2-pentoxy group, a 3-pentoxy group, a 2-methyl-1-butoxy group,a tert-pentoxy group, a 3-methyl-1-butoxy group, a 3-methyl-2-butoxygroup, or a neo-pentoxy group; alternatively, a methoxy group, an ethoxygroup, an isopropoxy group, a tert-butoxy group, or a neo-pentoxy group;alternatively, a methoxy group; alternatively, an ethoxy group;alternatively, an isopropoxy group; alternatively, a tert-butoxy group;or alternatively, a neo-pentoxy group. In an embodiment, each aroxysubstituent for any substituted R¹ group (general or specific)independently can be a phenoxy group, a toloxy group, a xyloxy group, ora 2,4,6-trimethylphenoxy group; alternatively, a phenoxy group;alternatively, a toloxy group; alternatively, a xyloxy group; oralternatively, a 2,4,6-trimethylphenoxy group. In an embodiment, eacharalkoxy substituent for any substituted R¹ group (general or specific)independently can be a benzoxy group.

In a non-limiting embodiment, R¹ can be a phenyl group, a 2-alkylphenylgroup, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group;alternatively, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenylgroup; alternatively, a 3-alkylphenyl group or a 3,5-dialkylphenylgroup; alternatively, a 2-alkylphenyl group or a 2,6-dialkylphenylgroup; alternatively, a 2-alkylphenyl group; alternatively, a3-alkylphenyl group; alternatively, a 4-alkylphenyl group;alternatively, a 2,4-dialkylphenyl group; alternatively, a2,6-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group; oralternatively, a 2,4,6-trialkylphenyl group. In another non-limitingembodiment, R¹ can be a napht-1-yl group, a naphth-2-yl group, a2-alkylnaphth-1-yl group, a 1-alkylnaphth-2-yl group, a3-alkylnapth-2-yl group, or a 1,3-dialkylnaphth-2-yl group;alternatively, a napht-1-yl group or a 2-alkylnaphth-1-yl group;alternatively, a naphth-2-yl group, a 1-alkylnaphth-2-yl group, a3-alkylnapth-2-yl group, or a 1,3-dialkylnaphth-2-yl group;alternatively, a napht-1-yl group; alternatively, a naphth-2-yl group;alternatively, a 2-alkylnaphth-1-yl group; alternatively, a1-alkylnaphth-2-yl group; alternatively, a 3-alkylnapth-2-yl group; oralternatively, a 1,3-dialkylnaphth-2-yl group. In other non-limitingembodiments, R¹ can be a cyclohexyl group, a 2-alkylcyclohexyl group, ora 2,6-dialkylcyclohexyl group; alternatively, a cyclopentyl group, a2-alkylcyclopentyl group, or a 2,5-dialkylcyclopentyl group;alternatively, a cyclohexyl group; alternatively, a 2-alkylcyclohexylgroup; alternatively, a 2,6-dialkylcyclohexyl group; alternatively, acyclopentyl group; alternatively, a 2-alkylcyclopentyl group; oralternatively, a 2,5-dialkylcyclopentyl group. Alkyl group substituentsare independently described herein and can be utilized, withoutlimitation, to further describe the alkylphenyl, dialkylphenyl,trialkylphenyl, naphthyl, dialkylnaphthyl, alkylcyclohexyl,dialkylcyclohexyl, alkylcyclopentyl, or dialkylcyclopentyl groups thatcan be utilized R¹. Generally, the alkyl substituents of a dialkyl ortrialkyl phenyl, naphthyl, cyclohexyl, or cyclopentyl group can be thesame; or alternatively, the alkyl substituents of a dialkyl or trialkylphenyl, naphthyl, cyclohexyl, or cyclopentyl group can be different.

In another non-limiting embodiment, R¹ can be a phenyl group, a2-alkoxyphenyl group, a 3-alkoxyphenyl group, a 4-alkoxyphenyl group, ora 3,5-dialkoxyphenyl group; alternatively, a 2-alkoxyphenyl group or a4-alkoxyphenyl group; alternatively, a 3-alkoxyphenyl group or a3,5-dialkoxyphenyl group; alternatively, a 2-alkoxyphenyl group;alternatively, a 3-alkoxyphenyl group; alternatively, a 4-alkoxyphenylgroup; alternatively, a 3,5-dialkoxyphenyl group. Alkoxy groupsubstituents are independently described herein and can be utilized,without limitation, to further describe the alkoxyphenyl ordialkoxyphenyl groups that can be utilized R¹. Generally, the alkoxysubstituents of a dialkoxyphenyl group can be the same; oralternatively, the alkoxy substituents of a dialkoxyphenyl group can bedifferent.

In other non-limiting embodiments, R¹ can be a phenyl group, a2-halophenyl group, a 3-halophenyl group, a 4-halophenyl group, a2,6-dihalophenyl group, or a 3,5-dialkylphenyl group; alternatively, a2-halophenyl group, a 4-halophenyl group, or a 2,6-dihalophenyl group;alternatively, a 2-halophenyl group or a 4-halophenyl group;alternatively, a 3-halophenyl group or a 3,5-dihalophenyl group;alternatively, a 2-halophenyl group; alternatively, a 3-halophenylgroup; alternatively, a 4-halophenyl group; alternatively, a2,6-dihalophenyl group; or alternatively, a 3,5-dihalophenyl group.Halides are independently described herein and can be utilized, withoutlimitation, to further describe the halophenyl or dihalophenyl groupsthat can be utilized R¹. Generally, the halides of a dihalophenyl groupcan be the same; or alternatively, the halides of a dihalophenyl groupcan be different.

In a non-limiting embodiment, R¹ can be a 2-methylphenyl group, a2-ethylphenyl group, a 2-n-propylphenyl group, a 2-isopropylphenylgroup, a 2-tert-butylphenyl group, a 3-methylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, a3,5-dimethyl group, or a 2,4,6-trimethylphenyl group; alternatively, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; alternatively, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, or a 2-isopropyl-6-methylphenyl group;alternatively, a 2-methylphenyl group; alternatively, a 2-ethylphenylgroup; alternatively, a 2-n-propylphenyl group; alternatively, a2-isopropylphenyl group; alternatively, a 2-tert-butylphenyl group;alternatively, a 3-methylphenyl group; alternatively, a2,6-dimethylphenyl group; alternatively, a 2,6-diethylphenyl group;alternatively, a 2,6-di-n-propylphenyl group; alternatively, a2,6-diisopropylphenyl group; alternatively, a 2,6-di-tert-butylphenylgroup; alternatively, a 2-isopropyl-6-methylphenyl group; alternatively,a 3,5-dimethylphenyl group; or alternatively, a 2,4,6-trimethylphenylgroup. In another non-limiting embodiment, R¹ can be a2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, a 2-tert-butylcyclohexyl group, a2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexyl group, a2,6-diisopropylcyclohexyl group, or a 2,6-di-tert-butylcyclohexyl group;alternatively, a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, or a 2-tert-butylcyclohexyl group;alternatively, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexylgroup, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group; alternatively, a 2-methylcyclohexylgroup; alternatively, a 2-ethylcyclohexyl group; alternatively, a2-isopropylcyclohexyl group; alternatively, a 2-tert-butylcyclohexylgroup; alternatively, a 2,6-dimethylcyclohexyl group; alternatively, a2,6-diethylcyclohexyl group; alternatively, a 2,6-diisopropylcyclohexylgroup; or alternatively, a 2,6-di-tert-butylcyclohexyl group. In anothernon-limiting embodiment, R¹ can be a 2-methylnaphth-1-yl group, a2-ethylnaphth-1-yl group, a 2-n-propylnaphth-1-yl group, a2-isopropylnaphth-1-yl group, or a 2-tert-butylnaphth-1-yl group;alternatively, a 2-methylnaphth-1-yl group; alternatively, a2-ethylnaphth-1-yl group; alternatively, a 2-n-propylnaphth-1-yl group;alternatively, a 2-isopropylnaphth-1-yl group; or alternatively, a2-tert-butylnaphth-1-yl group.

In a non-limiting embodiment, R¹ can be a 3-methoxyphenyl group, a3-ethoxyphenyl group, a 3-isopropoxyphenyl group, a 3-tert-butoxyphenylgroup, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a4-isopropoxyphenyl group, a 4-tert-butoxyphenyl group, a3,5-dimethoxyphenyl group, a 3,5-diethoxyphenyl group, a3,5-diisopropoxyphenyl group, or a 3,5-di-tert-butoxyphenyl group;alternatively, a 3-methoxyphenyl group, a 3-ethoxyphenyl group, a3-isopropoxyphenyl group, or a 3-tert-butoxyphenyl group; alternatively,a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenylgroup, or a 4-tert-butoxyphenyl group; or alternatively, a3,5-dimethoxyphenyl group, a 3,5-diethoxyphenyl group, a3,5-diisopropoxyphenyl group, or a 3,5-di-tert-butoxyphenyl group. Inother non-limiting embodiments, R¹ can be a 3-methoxyphenyl group;alternatively, a 3-ethoxyphenyl group; alternatively, a3-isopropoxyphenyl group; alternatively, a 3-tert-butoxyphenyl group;alternatively, a 4-methoxyphenyl group; alternatively, a 4-ethoxyphenylgroup; alternatively, a 4-isopropoxyphenyl group; alternatively, a4-tert-butoxyphenyl group; alternatively, a 3,5-dimethoxyphenyl group;alternatively, a 3,5-diethoxyphenyl group; alternatively, a3,5-diisopropoxyphenyl group; or alternatively, a3,5-di-tert-butoxyphenyl group.

Generally, R² can be an organyl group, an organyl group consistingessentially of inert functional groups, or a hydrocarbyl group. In anembodiment, R² can be a C₁ to C₃₀ organyl group; alternatively, a C₁ toC₂₀ organyl group; alternatively, a C₁ to C₁₅ organyl group;alternatively, a C₁ to C₁₀ organyl group; or alternatively, a C₁ to C₅organyl group. In an embodiment, R² can be a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups; alternatively, a C₁to C₂₀ organyl group consisting essentially of inert functional groups;alternatively, a C₁ to C₁₅ organyl group consisting essentially of inertfunctional groups; alternatively, a C₁ to C₁₀ organyl group consistingessentially of inert functional groups; or alternatively, a C₁ to C₅organyl group consisting essentially of inert functional groups. In anembodiment, R² can be a C₁ to C₃₀ hydrocarbyl group; alternatively, a C₁to C₂₀ hydrocarbyl group; alternatively, a C₁ to C₁₅ hydrocarbyl group;alternatively, a C₁ to C₁₀ hydrocarbyl group; or alternatively, a C₁ toC₅ hydrocarbyl group. In yet other embodiments, R² can be a C₃ to C₃₀aromatic group; alternatively, a C₃ to C₂₀ aromatic group;alternatively, a C₃ to C₁₅ aromatic group; or alternatively, a C₃ to C₁₀aromatic group.

In an aspect, R² can be a C₁ to C₃₀ alkyl group, a C₄ to C₃₀ cycloalkylgroup, a C₄ to C₃₀ substituted cycloalkyl group, a C₃ to C₃₀ aliphaticheterocyclic group, a C₃ to C₃₀ substituted aliphatic heterocyclicgroup, a C₆ to C₃₀ aryl group, a C₆ to C₃₀ substituted aryl group, a C₇to C₃₀ aralkyl group, a C₇ to C₃₀ substituted aralkyl group, a C₃ to C₃₀heteroaryl group, or a C₃ to C₃₀ substituted heteroaryl group;alternatively, a C₁ to C₃₀ alkyl group, a C₄ to C₃₀ cycloalkyl group, aC₄ to C₃₀ substituted cycloalkyl group, a C₆ to C₃₀ aryl group, a C₆ toC₃₀ substituted aryl group, a C₇ to C₃₀ aralkyl group, or a C₇ to C₃₀substituted aralkyl group; alternatively, a C₄ to C₃₀ cycloalkyl groupor a C₄ to C₃₀ substituted cycloalkyl group; alternatively, a C₃ to C₃₀aliphatic heterocyclic group or a C₃ to C₃₀ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₃₀ aryl group or a C₆ to C₃₀substituted aryl group; alternatively, a C₇ to C₃₀ aralkyl group or a C₇to C₃₀ substituted aralkyl group; alternatively, a C₃ to C₃₀ heteroarylgroup or a C₃ to C₃₀ substituted heteroaryl group; alternatively, a C₁to C₃₀ alkyl group; alternatively, a C₄ to C₃₀ cycloalkyl group;alternatively, a C₄ to C₃₀ substituted cycloalkyl group; alternatively,a C₃ to C₃₀ aliphatic heterocyclic group; alternatively, a C₃ to C₃₀substituted aliphatic heterocyclic group; alternatively, a C₆ to C₃₀aryl group; alternatively, a C₆ to C₃₀ substituted aryl group;alternatively, a C₇ to C₃₀ aralkyl group; alternatively, a C₇ to C₃₀substituted aralkyl group; alternatively, a C₃ to C₃₀ heteroaryl group;or alternatively, a C₃ to C₃₀ substituted heteroaryl group. In anembodiment, R² can be a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkylgroup, a C₄ to C₂₀ substituted cycloalkyl group, a C₃ to C₂₀ aliphaticheterocyclic group, a C₃ to C₂₀ substituted aliphatic heterocyclicgroup, a C₆ to C₂₀ aryl group, a C₆ to C₂₀ substituted aryl group, a C₇to C₂₀ aralkyl group, a C₇ to C₂₀ substituted aralkyl group, a C₃ to C₂₀heteroaryl group, or a C₃ to C₂₀ substituted heteroaryl group;alternatively, a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, a C₆ toC₂₀ substituted aryl group, a C₇ to C₂₀ aralkyl group, or a C₇ to C₂₀substituted aralkyl group; alternatively, a C₄ to C₂₀ cycloalkyl groupor a C₄ to C₂₀ substituted cycloalkyl group; alternatively, a C₃ to C₂₀aliphatic heterocyclic group or a C₃ to C₂₀ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₂₀ aryl group or a C₆ to C₂₀substituted aryl group; alternatively, a C₇ to C₂₀ aralkyl group or a C₇to C₂₀ substituted aralkyl group; alternatively, a C₃ to C₂₀ heteroarylgroup or a C₃ to C₂₀ substituted heteroaryl group; alternatively, a C₁to C₁₅ alkyl group; alternatively, a C₄ to C₂₀ cycloalkyl group;alternatively, a C₄ to C₂₀ substituted cycloalkyl group; alternatively,a C₃ to C₂₀ aliphatic heterocyclic group; alternatively, a C₃ to C₂₀substituted aliphatic heterocyclic group; alternatively, a C₆ to C₂₀aryl group; alternatively, a C₆ to C₂₀ substituted aryl group;alternatively, a C₇ to C₂₀ aralkyl group; alternatively, a C₇ to C₂₀substituted aralkyl group; alternatively, a C₃ to C₂₀ heteroaryl group;or alternatively, a C₃ to C₂₀ substituted heteroaryl group. In otherembodiments, R² can be a C₁ to C₁₀ alkyl group, a C₄ to C₁₅ cycloalkylgroup, a C₄ to C₁₅ substituted cycloalkyl group, a C₃ to C₁₅ aliphaticheterocyclic group, a C₃ to C₁₅ substituted aliphatic heterocyclicgroup, a C₆ to C₁₅ aryl group, a C₆ to C₁₅ substituted aryl group, a C₇to C₁₅ aralkyl group, a C₇ to C₁₅ substituted aralkyl group, a C₃ to C₁₅heteroaryl group, or a C₃ to C₁₅ substituted heteroaryl group;alternatively, a C₁ to C₁₀ alkyl group, a C₄ to C₁₅ cycloalkyl group, aC₄ to C₁₅ substituted cycloalkyl group, a C₆ to C₁₅ aryl group, a C₆ toC₁₅ substituted aryl group, a C₇ to C₁₅ aralkyl group, or a C₇ to C₁₅substituted aralkyl group; alternatively, a C₄ to C₁₅ cycloalkyl groupor a C₄ to C₁₅ substituted cycloalkyl group; alternatively, a C₃ to C₁₅aliphatic heterocyclic group or a C₃ to C₁₅ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₁₅ aryl group or a C₆ to C₁₅substituted aryl group; alternatively, a C₇ to C₁₅ aralkyl group or a C₇to C₁₅ substituted aralkyl group; alternatively, a C₃ to C₁₅ heteroarylgroup or a C₃ to C₁₅ substituted heteroaryl group; alternatively, a C₁to C₁₀ alkyl group; alternatively, a C₄ to C₁₅ cycloalkyl group;alternatively, a C₄ to C₁₅ substituted cycloalkyl group; alternatively,a C₃ to C₁₅ aliphatic heterocyclic group; alternatively, a C₃ to C₁₅substituted aliphatic heterocyclic group; alternatively, a C₆ to C₁₅aryl group; alternatively, a C₆ to C₁₅ substituted aryl group;alternatively, a C₇ to C₁₅ aralkyl group; alternatively, a C₇ to C₁₅substituted aralkyl group; alternatively, a C₃ to C₁₅ heteroaryl group;or alternatively, a C₃ to C₁₅ substituted heteroaryl group. In furtherembodiments, R² can be a C₁ to C₅ alkyl group.

In an embodiment, R² can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, an undecyl group, a dodecylgroup, a tridecyl group, a tetradecyl group, a pentadecyl group, ahexadecyl group, a heptadecyl group, an octadecyl group, or a nonadecylgroup; or alternatively, a methyl group, an ethyl group, a propyl group,a butyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, or a decyl group. In some embodiments, R² can be amethyl group, an ethyl group, an n-propyl group, an iso-propyl group, ann-butyl group, an iso-butyl group, a sec-butyl group, a tert-butylgroup, an n-pentyl group, an iso-pentyl group, a sec-pentyl group, or aneopentyl group; alternatively, a methyl group, an ethyl group, aniso-propyl group, a tert-butyl group, or a neopentyl group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, an n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.In some embodiments, the alkyl groups which can be utilized as R² can besubstituted. Each substituent of a substituted alkyl group independentlycan be a halogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Halogens and hydrocarboxy groupsthat can be utilized as substituents are independently disclosed herein(e.g. as substituents for substituted R¹ groups) and can be utilizedwithout limitation to further describe the substituted alkyl group whichcan be utilized as R².

In an embodiment, R² can be a cyclobutyl group, a substituted cyclobutylgroup, a cyclopentyl group, a substituted cyclopentyl group, acyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, asubstituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. In some embodiments, R² can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. In other embodiments, R² can be a cyclobutyl group ora substituted cyclobutyl group; alternatively, a cyclopentyl group or asubstituted cyclopentyl group; alternatively, a cyclohexyl group or asubstituted cyclohexyl group; alternatively, a cycloheptyl group or asubstituted cycloheptyl group; or alternatively, a cyclooctyl group or asubstituted cyclooctyl group. In further embodiments, R² can be acyclopentyl group; alternatively, a substituted cyclopentyl group; acyclohexyl group; or alternatively, a substituted cyclohexyl group.

In an embodiment, each substituent for a substituted cycloalkyl group(general or specific) that can be utilized as R² independently can be ahalogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, ahalogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituent for a substituted cycloalkyl group (general or specific)that can be utilized as R¹ independently can be a halogen, an alkylgroup, or an alkoxy group; alternatively, a halogen or an alkyl group;alternatively, a halogen or an alkoxy group; alternatively, an alkylgroup or an alkoxy group; alternatively, a halogen; alternatively, analkyl group; or alternatively, an alkoxy group. Halogens, hydrocarbylgroups, hydrocarboxy groups, alkyl group, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for a substitutedcycloalkyl group (general or specific) that can be utilized as R².

In an aspect, R² may have Structure G3:

wherein, the undesignated valency is attached to the central carbon atomof the N²-phosphinyl amidine group. Generally, R^(21c), R^(23c),R^(24c), and R^(25c) independently can be hydrogen or a non-hydrogensubstituent, and n can be an integer from 1 to 5. In an embodimentwherein R² has Structure G3, R^(21c), R^(23c), R^(24c), and R^(25c) canbe hydrogen and R^(22c) can be any non-hydrogen substituent disclosedherein; or alternatively, R^(21c), R^(23c), and R^(25c) can be hydrogenand R^(22c) and R^(24c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively, 3.

In an embodiment, R^(21c), R^(22c), R^(23c), R^(24c), and R^(25c)independently can be hydrogen, a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, hydrogen, a halogen, or a hydrocarbylgroup; alternatively, hydrogen, a halogen, or a hydrocarboxy group;alternatively, hydrogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, hydrogen or a halogen; alternatively, hydrogen or ahydrocarbyl group; or alternatively, hydrogen or a hydrocarboxy group.In some embodiments, R^(21c), R^(22c), R^(23c), R^(24c), and R^(25c)independently can be hydrogen, a halogen, an alkyl group, or an alkoxygroup; alternatively, hydrogen, a halogen, or an alkyl group;alternatively, hydrogen, a halogen, or an alkoxy group; alternatively,hydrogen, an alkyl group, or an alkoxy group; alternatively, hydrogen ora halogen; alternatively, hydrogen or an alkyl group; or alternatively,hydrogen or an alkoxy group. Halogens, hydrocarbyl groups, hydrocarboxygroups, alkyl group, and alkoxy groups that can be utilized assubstituents are independently disclosed herein (e.g. as substituentsfor substituted R¹ groups) and can be utilized without limitation tofurther describe the R² group having Structure G3.

In an embodiment, R² can be a phenyl group or a substituted phenylgroup. In some embodiments, R² can be a phenyl group; or alternatively,a substituted phenyl group. In an embodiment, the R² substituted phenylgroup can be a 2-substituted phenyl group, a 3-substituted phenyl group,a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other embodiments, the R²substituted phenyl group can be a 2-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group or a 2,4,6-trisubstituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.

In an embodiment, each substituent for a substituted phenyl R² groupindependently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, each substituent for a substituted phenyl R² groupindependently can be a halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, a halogen oran alkoxy group; alternatively, an alkyl group or an alkoxy group;alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Halogens, hydrocarbyl groups,hydrocarboxy groups, alkyl groups, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for the substitutedphenyl R² group.

In an aspect, R² can have Structure G4:

wherein the undesignated valency is attached to the N¹ nitrogen atom ofthe N²-phosphinyl amidine group. Generally, R²², R²³, R²⁴, R²⁵, and R²⁶independently can be hydrogen or a non-hydrogen substituent. In anembodiment wherein R² has Structure G4, R²², R²³, R²⁴, R²⁵, and R²⁶ canbe hydrogen, R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen and R²² can be anon-hydrogen substituent, R²², R²⁴, R²⁵, and R²⁶ can be hydrogen and R²³can be a non-hydrogen substituent, R²², R²³, R²⁵, and R²⁶ can behydrogen and R²⁴ can be a non-hydrogen substituent, R²³, R²⁵, and R²⁶can be hydrogen and R²² and R²⁴ can be non-hydrogen substituents, R²³,R²⁴, and R²⁵ can be hydrogen and R²² and R²⁶ can be non-hydrogensubstituents, R²², R²⁴, and R²⁶ can be hydrogen and R²³ and R²⁵ can benon-hydrogen substituents, or R²³ and R²⁵ can be hydrogen and R²², R²⁴,and R²⁶ can be non-hydrogen substituents. In some embodiments wherein R²has Structure G4, R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen and R²² can bea non-hydrogen substituent, R²², R²³, R²⁵, and R²⁶ can be hydrogen andR²⁴ can be a non-hydrogen substituent, R²³, R²⁵, and R²⁶ can be hydrogenand R²² and R²⁴ can be non-hydrogen substituents, R²³, R²⁴, and R²⁵ canbe hydrogen and R²² and R²⁶ can be non-hydrogen substituents, or R²³ andR²⁵ can be hydrogen and R²², R²⁴, and R²⁶ can be non-hydrogensubstituents; alternatively, R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen andR²² can be a non-hydrogen substituent, R²², R²³, R²⁵, and R²⁶ can behydrogen and R²⁴ can be a non-hydrogen substituent, R²³, R²⁵, and R²⁶can be hydrogen and R²² and R²⁴ can be non-hydrogen substituents, orR²³, R²⁴, and R²⁵ can be hydrogen and R²² and R²⁶ can be non-hydrogensubstituents; alternatively, R²², R²⁴, R²⁵, and R²⁶ can be hydrogen andR²³ can be a non-hydrogen substituent, or R²², R²⁴, and R²⁶ can behydrogen and R²³ and R²⁵ can be non-hydrogen substituents;alternatively, R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen and R²² can be anon-hydrogen substituent, or R²², R²³, R²⁵, and R²⁶ can be hydrogen andR²⁴ can be a non-hydrogen substituent; alternatively, R²³, R²⁵, and R²⁶can be hydrogen and R²² and R²⁴ can be non-hydrogen substituents, R²³,R²⁴, and R²⁵ can be hydrogen and R²² and R²⁶ can be non-hydrogensubstituents, or R²³ and R²⁵ can be hydrogen and R²², R²⁴, and R²⁶ canbe non-hydrogen substituents; or alternatively, R²³, R²⁵, and R²⁶ can behydrogen and R²² and R²⁴ can be non-hydrogen substituents, or R²³, R²⁴,and R²⁵ can be hydrogen and R²² and R²⁶ can be non-hydrogensubstituents. In other embodiments wherein R² has Structure G4, R²²,R²³, R²⁴, R²⁵, and R²⁶ can be hydrogen; alternatively, R²³, R²⁴, R²⁵,and R²⁶ can be hydrogen and R²² can be a non-hydrogen substituent;alternatively, R²², R²⁴, R²⁵, and R²⁶ can be hydrogen and R²³ can be anon-hydrogen substituent; alternatively, R²², R²³, R²⁵, and R²⁶ can behydrogen and R²⁴ can be a non-hydrogen substituent; alternatively, R²³,R²⁵, and R²⁶ can be hydrogen and R²² and R²⁴ can be non-hydrogensubstituents; alternatively, R²³, R²⁴, and R²⁵ can be hydrogen and R²²and R²⁶ can be non-hydrogen substituents; alternatively, R²², R²⁴, andR²⁶ can be hydrogen and R²³ and R²⁵ and can be non-hydrogensubstituents; or alternatively, R²³ and R²⁵ can be hydrogen and R²²,R²⁴, and R²⁶ can be non-hydrogen substituents.

In an embodiment, the non-hydrogen substituents that can be utilized asR²², R²³, R²⁴, R²⁵, and R²⁶ in the R² group having Structure G4independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, the non-hydrogen substituents that can be utilized as R²²,R²³, R²⁴, R²⁵, and R²⁶ in the R² group having Structure G4 independentlycan be a halogen, an alkyl group, or an alkoxy group; alternatively, ahalogen or an alkyl group; alternatively, a halogen or an alkoxy group;alternatively, an alkyl group or an alkoxy group; alternatively, ahalogen; alternatively, an alkyl group; or alternatively, an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein (e.g. as substituents for substituted R¹ groups) andcan be utilized without limitation to further describe the R² grouphaving Structure G4.

In an aspect, R² can be a benzyl group, a substituted benzyl group, a1-phenyleth-1-yl group, a substituted 1-phenyleth-1-yl, a2-phenyleth-1-yl group, or a substituted 2-phenyleth-1-yl group. In anembodiment, R² can be a benzyl group, or a substituted benzyl group;alternatively, a 1-phenyleth-1-yl group or a substituted1-phenyleth-1-yl; alternatively, a 2-phenyleth-1-yl group or asubstituted 2-phenyleth-1-yl group; or alternatively, a benzyl group, a1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group. In someembodiments, R² can be a benzyl group; alternatively, a substitutedbenzyl group; alternatively, a 1-phenyleth-1-yl group; alternatively, asubstituted 1-phenyleth-1-yl; alternatively, a 2-phenyleth-1-yl group;or alternatively, a substituted 2-phenyleth-1-yl group.

In an embodiment, each substituent for a substituted benzyl group, a1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group (general orspecific) that can be utilized as R² independently can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituent for a substituted benzyl group, 1-phenyleth-1-yl group, or a2-phenyleth-1-yl group (general or specific) that can be utilized as R²independently can be halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, a halogen oran alkoxy group; alternatively, an alkyl group or an alkoxy group;alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Halogens, hydrocarbyl groups,hydrocarboxy groups, alkyl groups, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for the substitutedbenzyl group, 1-phenyleth-1-yl group, or a 2-phenyleth-1-yl group(general or specific) that can be utilized as R².

In an aspect, R² can be a pyridinyl group, a substituted pyridinylgroup, a furyl group, a substituted furyl group, a thienyl group, or asubstituted thienyl group. In an embodiment, R² can be a pyridinyl groupor a substituted pyridinyl group; alternatively, a furyl group or asubstituted furyl group; or alternatively, a thienyl group or asubstituted thienyl group. In some embodiments, R² can be a pyridinylgroup, a furyl group, or a thienyl group. In other embodiments, R² canbe a pyridinyl group; alternatively, a substituted pyridinyl group;alternatively, a furyl group; alternatively, a substituted furyl group;alternatively, a thienyl group; or alternatively, a substituted thienylgroup.

In an embodiment, the pyridinyl (or substituted pyridinyl) R² group canbe a pyridin-2-yl group, a substituted pyridin-2-yl group, apyridin-3-yl group, a substituted pyridin-3-yl group, a pyridin-4-ylgroup, or a substituted pyridin-4-yl group; alternatively, apyridin-2-yl group, a pyridin-3-yl group, or a pyridin-4-yl group. Insome embodiments, the pyridinyl (or substituted pyridinyl) R² group canbe a pyridin-2-yl group or a substituted pyridin-2-yl group;alternatively, a pyridin-3-yl group or a substituted pyridin-3-yl group;alternatively, a pyridin-4-yl group or a substituted pyridin-4-yl group;alternatively, a pyridin-2-yl group; alternatively, a substitutedpyridin-2-yl group; alternatively, a pyridin-3-yl group; alternatively,a substituted pyridin-3-yl group; alternatively, a pyridin-4-yl group;or alternatively, a substituted pyridin-4-yl group. In an embodiment,the substituted pyridinyl R² group can be a 2-substituted pyridin-3-ylgroup, a 4-substituted pyridin-3-yl group, a 5-substituted pyridin-3-ylgroup, a 6-substituted pyridin-3-yl group, a 2,4-disubstitutedpyridin-3-yl group, a 2,6-disubstituted pyridin-3-yl group, or a2,4,6-trisubstituted pyridin-3-yl group; alternatively, a 2-substitutedpyridin-3-yl group, a 4-substituted pyridin-3-yl group, or a6-substituted pyridin-3-yl group; alternatively, a 2,4-disubstitutedpyridin-3-yl group or a 2,6-disubstituted pyridin-3-yl group;alternatively, a 2-substituted pyridin-3-yl group; alternatively, a4-substituted pyridin-3-yl group; alternatively, a 5-substitutedpyridin-3-yl group; alternatively, a 6-substituted pyridin-3-yl group;alternatively, a 2,4-disubstituted pyridin-3-yl group; alternatively, a2,6-disubstituted pyridin-3-yl group; or alternatively, a2,4,6-trisubstituted pyridin-3-yl group. In an embodiment, thesubstituted pyridinyl R² group can be a 2-substituted pyridin-4-ylgroup, a 3-substituted pyridin-4-yl group, a 5-substituted pyridin-4-ylgroup, a 6-substituted pyridin-4-yl group, a 2,6-disubstitutedpyridin-4-yl group, or a 3,5-disubstituted pyridin-4-yl group;alternatively, a 2-substituted pyridin-4-yl group or a 6-substitutedpyridin-4-yl group; alternatively, a 3-substituted pyridin-4-yl group ora 5-substituted pyridin-4-yl group; alternatively, a 2-substitutedpyridin-4-yl group; alternatively, a 3-substituted pyridin-4-yl group;alternatively, a 5-substituted pyridin-4-yl group; alternatively, a6-substituted pyridin-4-yl group; alternatively, a 2,6-disubstitutedpyridin-4-yl group; or alternatively, a 3,5-disubstituted pyridin-4-ylgroup.

In an embodiment, the furyl (or substituted furyl) R² group can be afur-2-yl group, a substituted fur-2-yl group, a fur-3-yl group, or asubstituted fur-3-yl group; alternatively, a fur-2-yl or a fur-3-ylgroup. In some embodiments, the furyl (or substituted furyl) R² groupcan be a fur-2-yl group or a substituted fur-2-yl group; alternatively,a fur-3-yl group or a substituted fur-3-yl group; alternatively, afur-2-yl group; alternatively, a substituted fur-2-yl group;alternatively, a fur-3-yl group; or alternatively, a substitutedfur-3-yl group. In an embodiment, the substituted furyl R² group can bea 2-substituted fur-3-yl group, a 4-substituted fur-3-yl group, or a2,4-disubstituted fur-3-yl group; alternatively, a 2-substitutedfur-3-yl group; alternatively, a 4-substituted fur-3-yl group; oralternatively, a 2,4-disubstituted fur-3-yl group.

In an embodiment, the thienyl (or substituted thienyl) R² group can be athien-2-yl group, a substituted thien-2-yl group, a thien-3-yl group, ora substituted thien-3-yl group; alternatively, a thien-2-yl group or athien-3-yl group. In some embodiments, the thienyl (or substitutedthienyl) R² group can be a thien-2-yl group or a substituted thien-2-ylgroup; alternatively, a thien-3-yl group or a substituted thien-3-ylgroup; alternatively, a thien-2-yl group; alternatively, a substitutedthien-2-yl group; alternatively, a thien-3-yl group; or alternatively, asubstituted thien-3-yl group. In an embodiment, the substituted thienylR² group can be a 2-substituted thien-3-yl group, a 4-substitutedthien-3-yl group, or a 2,4-disubstituted thien-3-yl group;alternatively, a 2-substituted thien-3-yl group; alternatively, a4-substituted thien-3-yl group; or alternatively, a 2,4-disubstitutedthien-3-yl group.

In an embodiment, each substituent for a substituted pyridinyl, furyl,or thienyl groups (general or specific) that can be utilized as R²independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, each substituent for a substituted pyridinyl, furyl, and/oror thienyl group (general or specific) that can be utilized as R²independently can be halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, a halogen oran alkoxy group; alternatively, an alkyl group or an alkoxy group;alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Halogens, hydrocarbyl groups,hydrocarboxy groups, alkyl groups, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for the substitutedpyridinyl, furyl, and/or thienyl groups (general or specific) that canbe utilized as R².

General and specific non-hydrogen substituents of a substitutedcycloalkyl group (general or specific), a substituted aliphaticheterocyclic group (general or specific), a substituted cycloheterylgroup (general or specific), a substituted aromatic group (general orspecific), a substituted aryl group (general or specific), a substitutedaralkyl group (general or specific), a substituted heteroaryl group(general or specific), or a substituted arylheteryl group (general orspecific) are disclosed herein. These general and specific non-hydrogensubstituents can be utilized, without limitation, to further describethe substituted cycloalkyl groups (general or specific), substitutedaliphatic heterocyclic groups (general or specific), substitutedcycloheteryl groups (general or specific), substituted aromatic groups(general or specific), substituted aryl groups (general or specific),substituted heteroaryl groups (general or specific), substitutedarylheteryl group (general or specific), or any other general orspecific group which can be utilized as R².

In a non-limiting embodiment, R² can be a phenyl group, a 2-alkylphenylgroup, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group;alternatively, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenylgroup; alternatively, a 3-alkylphenyl group or a 3,5-dialkylphenylgroup; alternatively, a 2-alkylphenyl group or a 2,6-dialkylphenylgroup; alternatively, a 2-alkylphenyl group; alternatively, a3-alkylphenyl group; alternatively, a 4-alkylphenyl group;alternatively, a 2,4-dialkylphenyl group; alternatively, a2,6-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group; oralternatively, a 2,4,6-trialkylphenyl group. In another non-limitingembodiment, R² can be a phenyl group, a 2-alkoxyphenyl group, a3-alkoxyphenyl group, a 4-alkoxyphenyl group, or 3,5-dialkoxyphenylgroup; alternatively, a 2-alkoxyphenyl group or a 4-alkoxyphenyl group;alternatively, a 3-alkoxyphenyl group or 3,5-dialkoxyphenyl group;alternatively, a 2-alkoxyphenyl group; alternatively, 3-alkoxyphenylgroup; alternatively, a 4-alkoxyphenyl group; alternatively,3,5-dialkoxyphenyl group. In other non-limiting embodiments, R² can be aphenyl group, a 2-halophenyl group, a 3-halophenyl group, a 4-halophenylgroup, a 2,6-dihalophenyl group, or a 3,5-dialkylphenyl group;alternatively, a 2-halophenyl group, a 4-halophenyl group, or a2,6-dihalophenyl group; alternatively, a 2-halophenyl group or a4-halophenyl group; alternatively, a 3-halophenyl group or a3,5-dihalophenyl group; alternatively, a 2-halophenyl group;alternatively, a 3-halophenyl group; alternatively, a 4-halophenylgroup; alternatively, a 2,6-dihalophenyl group; or alternatively, a3,5-dihalophenyl group. Halides, alkyl group substituents, and alkoxygroup substituents are independently described herein and can beutilized, without limitation, to further describe the alkylphenyl,dialkylphenyl, trialkylphenyl, alkoxyphenyl, dialkoxyphenyl, halophenyl,or dihalophenyl groups that can be utilized R². Generally, the halides,alkyl substituents, or alkoxy substituents of a dialkyl, trialkylphenyl, dialkoxyphenyl, or dihalophenyl groups can be the same; oralternatively, the halo, alkyl substituents, or alkoxy substituents ofalkylphenyl, dialkylphenyl, trialkylphenyl, dialkoxyphenyl, ordihalophenyl groups can be different.

In a non-limiting embodiment, R² can be a 2-methylphenyl group, a2-ethylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenylgroup, a 4-methylphenyl group, a 4-ethylphenyl group, a4-isopropylphenyl group, or a 4-tert-butylphenyl group; alternatively, a2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group,or a 2-tert-butylphenyl group; alternatively, a 4-methylphenyl group, a4-ethylphenyl group, a 4-isopropylphenyl group, or a 4-tert-butylphenylgroup; alternatively, a 2-methylphenyl group; alternatively, a2-ethylphenyl group; alternatively, a 2-isopropylphenyl group;alternatively, a 2-tert-butylphenyl group; alternatively, a4-methylphenyl group; alternatively, a 4-ethylphenyl group;alternatively, a 4-isopropylphenyl group; or alternatively, a4-tert-butylphenyl group. In another non-limiting embodiment, R² can bea 2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenylgroup, a 2-tert-butoxyphenyl group, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group; alternatively, a 2-methoxyphenyl group, a2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a2-tert-butoxyphenyl group; alternatively, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group; alternatively, a 2-methoxyphenyl group;alternatively, a 2-ethoxyphenyl group; alternatively, a2-isopropoxyphenyl group; alternatively, a 2-tert-butoxyphenyl group;alternatively, a 4-methoxyphenyl group; alternatively, a 4-ethoxyphenylgroup; alternatively, a 4-isopropoxyphenyl group; or alternatively, a4-tert-butoxyphenyl group. In other non-limiting embodiments, R² can bea 2-fluorophenyl group, a 2-chlorophenyl group, a 3-fluorophenyl group,a 3-chlorophenyl group, a 4-fluorophenyl group, a 4-chlorophenyl group,a 3,5-difluorophenyl group, or a 3,5-dichlorophenyl group;alternatively, a 2-fluorophenyl group or a 2-chlorophenyl group;alternatively, a 3-fluorophenyl group or a 3-chlorophenyl group;alternatively, a 4-fluorophenyl group or a 4-chlorophenyl group;alternatively, a 3,5-difluorophenyl group or a 3,5-dichlorophenyl group;alternatively, a 3-fluorophenyl group, a 3-chlorophenyl group, a3,5-difluorophenyl group or a 3,5-dichlorophenyl group; alternatively, a3-fluorophenyl group or a 3,5-difluorophenyl group; alternatively, a2-fluorophenyl group; alternatively, a 2-chlorophenyl group;alternatively, a 3-fluorophenyl group; alternatively, a 3-chlorophenylgroup; alternatively, a 4-fluorophenyl group; alternatively, a4-chlorophenyl; alternatively, a 3,5-difluorophenyl group; oralternatively, a 3,5-dichlorophenyl group.

In an aspect, R³ can be hydrogen. In another aspect, R³ can be anorganyl group, an organyl group consisting essentially of inertfunctional groups, or a hydrocarbyl group. In an embodiment, R³ can be aC₁ to C₃₀ organyl group; alternatively, a C₁ to C₂₀ organyl group;alternatively, a C₁ to C₁₅ organyl group; alternatively, a C₁ to C₁₀organyl group; or alternatively, a C₁ to C₅ organyl group. In anembodiment, R³ can be a C₁ to C₃₀ organyl group consisting essentiallyof inert functional groups; alternatively, a C₁ to C₂₀ organyl groupconsisting essentially of inert functional groups; alternatively, a C₁to C₁₅ organyl group consisting essentially of inert functional groups;alternatively, a C₁ to C₁₀ organyl group consisting essentially of inertfunctional groups; or alternatively, a C₁ to C₅ organyl group consistingessentially of inert functional groups. In an embodiment, R³ can be a C₁to C₃₀ hydrocarbyl group; alternatively, a C₁ to C₂₀ hydrocarbyl group;alternatively, a C₁ to C₁₅ hydrocarbyl group; alternatively, a C₁ to C₁₀hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarbyl group. Inyet other embodiments, R³ may be a C₃ to C₃₀ aromatic group;alternatively, a C₃ to C₂₀ aromatic group; alternatively, a C₃ to C₁₅aromatic group; or alternatively, a C₃ to C₁₀ aromatic group.

In an aspect, R³ can be a C₁ to C₃₀ alkyl group, a C₄ to C₃₀ cycloalkylgroup, a C₄ to C₃₀ substituted cycloalkyl group, a C₃ to C₃₀ aliphaticheterocyclic group, a C₃ to C₃₀ substituted aliphatic heterocyclicgroup, a C₆ to C₃₀ aryl group, a C₆ to C₃₀ substituted aryl group, a C₃to C₃₀ heteroaryl group, or a C₃ to C₃₀ substituted heteroaryl group;alternatively, a C₁ to C₃₀ alkyl group, a C₄ to C₃₀ cycloalkyl group, aC₄ to C₃₀ substituted cycloalkyl group, a C₆ to C₃₀ aryl group, or a C₆to C₃₀ substituted aryl group; alternatively, a C₄ to C₃₀ cycloalkylgroup or a C₄ to C₃₀ substituted cycloalkyl group; alternatively, a C₃to C₃₀ aliphatic heterocyclic group or a C₃ to C₃₀ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₃₀ aryl group or a C₆ to C₃₀substituted aryl group; alternatively, a C₃ to C₃₀ heteroaryl group or aC₃ to C₃₀ substituted heteroaryl group; alternatively, a C₁ to C₃₀ alkylgroup; alternatively, a C₄ to C₃₀ cycloalkyl group; alternatively, a C₄to C₃₀ substituted cycloalkyl group; alternatively, a C₃ to C₃₀aliphatic heterocyclic group; alternatively, a C₃ to C₃₀ substitutedaliphatic heterocyclic group; alternatively, a C₆ to C₃₀ aryl group;alternatively, a C₆ to C₃₀ substituted aryl group; alternatively, a C₃to C₃₀ heteroaryl group; or alternatively, a C₃ to C₃₀ substitutedheteroaryl group. In an embodiment, R³ can be a C₁ to C₁₅ alkyl group, aC₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, aC₃ to C₂₀ aliphatic heterocyclic group, a C₃ to C₂₀ substitutedaliphatic heterocyclic group, a C₆ to C₂₀ aryl group, a C₆ to C₂₀substituted aryl group, a C₃ to C₂₀ heteroaryl group, or a C₃ to C₂₀substituted heteroaryl group; alternatively, a C₁ to C₁₅ alkyl group, aC₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, aC₆ to C₂₀ aryl group, or a C₆ to C₂₀ substituted aryl group;alternatively, a C₄ to C₂₀ cycloalkyl group or a C₄ to C₂₀ substitutedcycloalkyl group; alternatively, a C₃ to C₂₀ aliphatic heterocyclicgroup or a C₃ to C₂₀ substituted aliphatic heterocyclic group;alternatively, a C₆ to C₂₀ aryl group or a C₆ to C₂₀ substituted arylgroup; alternatively, a C₃ to C₂₀ heteroaryl group or a C₃ to C₂₀substituted heteroaryl group; alternatively, a C₁ to C₁₅ alkyl group;alternatively, a C₄ to C₂₀ cycloalkyl group; alternatively, a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₃ to C₂₀ aliphaticheterocyclic group; alternatively, a C₃ to C₂₀ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₂₀ aryl group;alternatively, a C₆ to C₂₀ substituted aryl group; alternatively, a C₃to C₂₀ heteroaryl group; or alternatively, a C₃ to C₂₀ substitutedheteroaryl group. In other embodiments, R³ can be a C₁ to C₁₀ alkylgroup, a C₄ to C₁₅ cycloalkyl group, a C₄ to C₁₅ substituted cycloalkylgroup, a C₃ to C₁₅ aliphatic heterocyclic group, a C₃ to C₁₅ substitutedaliphatic heterocyclic group, a C₆ to C₁₅ aryl group, a C₆ to C₁₅substituted aryl group, a C₃ to C₁₅ heteroaryl group, or a C₃ to C₁₅substituted heteroaryl group; alternatively, a C₁ to C₁₀ alkyl group, aC₄ to C₁₅ cycloalkyl group, a C₄ to C₁₅ substituted cycloalkyl group, aC₆ to C₁₅ aryl group, or a C₆ to C₁₅ substituted aryl group;alternatively, a C₄ to C₁₅ cycloalkyl group or a C₄ to C₁₅ substitutedcycloalkyl group; alternatively, a C₃ to C₁₅ aliphatic heterocyclicgroup or a C₃ to C₁₅ substituted aliphatic heterocyclic group;alternatively, a C₆ to C₁₅ aryl group or a C₆ to C₁₅ substituted arylgroup; alternatively, a C₃ to C₁₅ heteroaryl group or a C₃ to C₁₅substituted heteroaryl group; alternatively, a C₁ to C₁₀ alkyl group;alternatively, a C₄ to C₁₅ cycloalkyl group; alternatively, a C₄ to C₁₅substituted cycloalkyl group; alternatively, a C₃ to C₁₅ aliphaticheterocyclic group; alternatively, a C₃ to C₁₅ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₁₅ aryl group;alternatively, a C₆ to C₁₅ substituted aryl group; alternatively, a C₃to C₁₅ heteroaryl group; or alternatively, a C₃ to C₁₅ substitutedheteroaryl group. In further embodiments, R³ can be a C₁ to C₅ alkylgroup

In an embodiment, R³ can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, a undecyl group, a dodecylgroup, a tridecyl group, a tetradecyl group, a pentadecyl group, ahexadecyl group, a heptadecyl group, an octadecyl group, or a nonadecylgroup; or alternatively, a methyl group, an ethyl group, a propyl group,a butyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, or a decyl group. In some embodiments, R³ can be amethyl group, an ethyl group, an n-propyl group, an iso-propyl group, ann-butyl group, an iso-butyl group, a sec-butyl group, a tert-butylgroup, an n-pentyl group, an iso-pentyl group, a sec-pentyl group, or aneopentyl group; alternatively, a methyl group, an ethyl group, aniso-propyl group, a tert-butyl group, or a neopentyl group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, an n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.In some embodiments, the alkyl groups which can be utilized as R³ can besubstituted. Each substituent of a substituted alkyl group independentlycan be a halogen or a hydrocarboxy group; alternatively, a halogen; oralternatively, a hydrocarboxy group. Halogens and hydrocarboxy groupsthat can be utilized as substituents are independently disclosed herein(e.g. as substituents for substituted R¹ groups) and can be utilizedwithout limitation to further describe the substituted alkyl group whichcan be utilized as R³.

In an embodiment, R³ can be a cyclobutyl group, a substituted cyclobutylgroup, a cyclopentyl group, a substituted cyclopentyl group, acyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group, asubstituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. In some embodiments, R³ can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. In other embodiments, R³ can be a cyclobutyl group ora substituted cyclobutyl group; alternatively, a cyclopentyl group or asubstituted cyclopentyl group; alternatively, a cyclohexyl group or asubstituted cyclohexyl group; alternatively, a cycloheptyl group or asubstituted cycloheptyl group; or alternatively, a cyclooctyl group or asubstituted cyclooctyl group. In further embodiments, R³ can be acyclopentyl group; alternatively, a substituted cyclopentyl group; acyclohexyl group; or alternatively, a substituted cyclohexyl group.

In an embodiment, each substituent for a substituted cycloalkyl group(general or specific) that can be utilized as R³ independently can be ahalogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, ahalogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a hydrocarbyl group or a hydrocarboxygroup; alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituent for a substituted cycloalkyl group (general or specific)that can be utilized as R³ independently can be a halogen, an alkylgroup, or an alkoxy group; alternatively, an alkyl group or an alkoxygroup; alternatively, a halogen or an alkyl group; alternatively, ahalogen or an alkoxy group; alternatively, a halogen; alternatively, analkyl group; or alternatively, an alkoxy group. Halogens, hydrocarbylgroups, hydrocarboxy groups, alkyl group, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for a substitutedcycloalkyl group (general or specific) that can be utilized as R³.

In an aspect, R³ can have Structure G5:

wherein, the undesignated valency is attached to the N² nitrogen atom ofthe N²-phosphinyl amidine group. Generally, R^(31c), R^(32c), R^(33c),R^(34c), and R^(35c) independently can be hydrogen or a non-hydrogensubstituent, and n can be an integer from 1 to 5. In an embodimentwherein R³ has Structure G5, R^(31c), R^(33c), R^(34c), and R^(35c) canbe hydrogen and R^(32c) can be any non-hydrogen substituent disclosedherein; or alternatively, R^(31c), R^(33c), and R^(35c) can be hydrogenand R^(32c) and R^(34c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively, 3.

In an embodiment, R^(31c), R^(32c), R^(33c), R^(34c), and R^(35c)independently can be hydrogen, a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, hydrogen, a halogen, or a hydrocarbylgroup; alternatively, hydrogen, a halogen, or a hydrocarboxy group;alternatively, hydrogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, hydrogen or a halogen; alternatively, hydrogen or ahydrocarbyl group; or alternatively, hydrogen or a hydrocarboxy group.In some embodiments, R^(31c), R^(32c), R^(33c), R^(34c), and R^(35c)independently can be hydrogen, a halogen, an alkyl group, or an alkoxygroup; alternatively, hydrogen, a halogen, or an alkyl group;alternatively, hydrogen, a halogen, or an alkoxy group; alternatively,an alkyl group or an alkoxy group; alternatively, hydrogen or a halogen;alternatively, hydrogen or an alkyl group; or alternatively, hydrogen oran alkoxy group. Halogens, hydrocarbyl groups, hydrocarboxy groups,alkyl groups, and alkoxy groups that can be utilized as substituents areindependently disclosed herein (e.g. as substituents for substituted R¹groups) and can be utilized without limitation to further describe theR³ group having Structure G5.

In an embodiment, R³ can be a phenyl group or a substituted phenylgroup. In some embodiments, R³ can be a phenyl group; or alternatively,a substituted phenyl group. In an embodiment, the R³ substituted phenylgroup can be a 2-substituted phenyl group, a 3-substituted phenyl group,a 4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other embodiments, the R³substituted phenyl group can be a 2-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group or a 2,4,6-trisubstituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.

In an embodiment, each substituent for a substituted phenyl R³ groupindependently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, each substituent for a substituted phenyl R³ groupindependently can be a halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, a halogen oran alkoxy group; alternatively, an alkyl group or an alkoxy group;alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Halogens, hydrocarbyl groups,hydrocarboxy groups, alkyl groups, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for the substitutedphenyl R³ group.

In an aspect, R³ can have Structure G6:

wherein the undesignated valency is attached to the N¹ nitrogen atom ofthe N²-phosphinylamidine group. Generally, R³², R³³, R³⁴, R³⁵, and R³⁶independently can be hydrogen or a non-hydrogen substituent. In anembodiment wherein R³ has Structure G6, R³², R³³, R³⁴, R³⁵, and R³⁶ canbe hydrogen, R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen and R³² can be anon-hydrogen substituent, R³², R³⁴, R³⁵, and R³⁶ can be hydrogen and R³³can be a non-hydrogen substituent, R³², R³³, R³⁵, and R³⁶ can behydrogen and R³⁴ can be a non-hydrogen substituent, R³³, R³⁵, and R³⁶can be hydrogen and R³² and R³⁴ can be non-hydrogen substituents, R³³,R³⁴, and R³⁵ can be hydrogen and R³² and R³⁶ can be non-hydrogensubstituents, R³², R³⁴, and R³⁶ can be hydrogen and R³³ and R³⁵ can benon-hydrogen substituents, or R³³ and R³⁵ can be hydrogen and R³², R³⁴,and R³⁶ can be non-hydrogen substituents. In some embodiments wherein R³has Structure G6, R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen and R³² can bea non-hydrogen substituent, R³², R³³, R³⁵, and R³⁶ can be hydrogen andR³⁴ can be a non-hydrogen substituent, R³³, R³⁵, and R³⁶ can be hydrogenand R³² and R³⁴ can be non-hydrogen substituents, R³³, R³⁴, and R³⁵ canbe hydrogen and R³² and R³⁶ can be non-hydrogen substituents, or R³³ andR³⁵ can be hydrogen and R³², R³⁴, and R³⁶ can be non-hydrogensubstituents; alternatively, R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen andR³² can be a non-hydrogen substituent, R³², R³³, R³⁵, and R³⁶ can behydrogen and R³⁴ can be a non-hydrogen substituent, R³³, R³⁵, and R³⁶can be hydrogen and R³² and R³⁴ can be non-hydrogen substituents, orR³³, R³⁴, and R³⁵ can be hydrogen and R³² and R³⁶ can be non-hydrogensubstituents; alternatively, R³², R³⁴, R³⁵, and R³⁶ can be hydrogen andR³³ can be a non-hydrogen substituent, or R³², R³⁴, and R³⁶ can behydrogen and R³³ and R³⁵ can be non-hydrogen substituents;alternatively, R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen and R³² can be anon-hydrogen substituent, or R³², R³³, R³⁵, and R³⁶ can be hydrogen andR³⁴ can be a non-hydrogen substituent; alternatively, R³³, R³⁵, and R³⁶can be hydrogen and R³² and R³⁴ can be non-hydrogen substituents, R³³,R³⁴, and R³⁵ can be hydrogen and R³² and R³⁶ can be non-hydrogensubstituents, or R³³ and R³⁵ can be hydrogen and R³², R³⁴, and R³⁶ canbe non-hydrogen substituents; or alternatively, R³³, R³⁵, and R³⁶ can behydrogen and R³² and R³⁴ can be non-hydrogen substituents, or R³³, R³⁴,and R³⁵ can be hydrogen and R³² and R³⁶ can be non-hydrogensubstituents. In other embodiments wherein R³ has Structure G6, R³²,R³³, R³⁴, R³⁵, and R³⁶ can be hydrogen; alternatively, R³³, R³⁴, R³⁵,and R³⁶ can be hydrogen and R³² can be a non-hydrogen substituent;alternatively, R³², R³⁴, R³⁵, and R³⁶ can be hydrogen and R³³ can be anon-hydrogen substituent; alternatively, R³², R³³, R³⁵, and R³⁶ can behydrogen and R³⁴ can be a non-hydrogen substituent; alternatively, R³³,R³⁵, and R³⁶ can be hydrogen and R³² and R³⁴ can be non-hydrogensubstituents; alternatively, R³³, R³⁴, and R³⁵ can be hydrogen and R³²and R³⁶ can be non-hydrogen substituents; alternatively, R³², R³⁴, andR³⁶ can be hydrogen and R³³ and R³⁵ and can be non-hydrogensubstituents; or alternatively, R³³ and R³⁵ can be hydrogen and R³²,R³⁴, and R³⁶ can be non-hydrogen substituents.

In an embodiment, the non-hydrogen substituents that can be utilized asR³², R³³, R³⁴, R³⁵, and R³⁶ in the R³ group having Structure G6independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, the non-hydrogen substituents that can be utilized as R³²,R³³, R³⁴, R³⁵, and R³⁶ in the R³ group having Structure G6 independentlycan be a halogen, an alkyl group, or an alkoxy group; alternatively,halogen, or an alkyl group; alternatively, a halogen or an alkoxy group;alternatively, an alkyl group or an alkoxy group; alternatively, ahalogen; alternatively, an alkyl group; or alternatively, or an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein (e.g. as substituents for substituted R¹ groups) andcan be utilized without limitation to further describe the R³ grouphaving Structure G6.

In an aspect, R³ can be a pyridinyl group, a substituted pyridinylgroup, a furyl group, a substituted furyl group, a thienyl group, or asubstituted thienyl group. In an embodiment, R³ can be a pyridinyl groupor a substituted pyridinyl group; alternatively, a furyl group or asubstituted furyl group; or alternatively, a thienyl group or asubstituted thienyl group. In some embodiments, R³ can be a pyridinylgroup, a furyl group, or a thienyl group. In other embodiments, R³ canbe a pyridinyl group; alternatively, a substituted pyridinyl group;alternatively, a furyl group; alternatively, a substituted furyl group;alternatively, a thienyl group; or alternatively, a substituted thienylgroup.

In an embodiment, the pyridinyl (or substituted pyridinyl) R³ group canbe a pyridin-2-yl group, a substituted pyridin-2-yl group, apyridin-3-yl group, a substituted pyridin-3-yl group, a pyridin-4-ylgroup, or a substituted pyridin-4-yl group; alternatively, apyridin-2-yl group, a pyridin-3-yl group, or a pyridin-4-yl group. Insome embodiments, the pyridinyl (or substituted pyridinyl) R³ group canbe a pyridin-2-yl group or a substituted pyridin-2-yl group;alternatively, a pyridin-3-yl group or a substituted pyridin-3-yl group;alternatively, a pyridin-4-yl group or a substituted pyridin-4-yl group;alternatively, a pyridin-2-yl group; alternatively, a substitutedpyridin-2-yl group; alternatively, a pyridin-3-yl group; alternatively,a substituted pyridin-3-yl group; alternatively, a pyridin-4-yl group;or alternatively, a substituted pyridin-4-yl group. In an embodiment,the substituted pyridinyl R³ group can be a 2-substituted pyridin-3-ylgroup, a 4-substituted pyridin-3-yl group, a 5-substituted pyridin-3-ylgroup, a 6-substituted pyridin-3-yl group, a 2,4-disubstitutedpyridin-3-yl group, a 2,6-disubstituted pyridin-3-yl group, or a2,4,6-trisubstituted pyridin-3-yl group; alternatively, a 2-substitutedpyridin-3-yl group, a 4-substituted pyridin-3-yl group, or a6-substituted pyridin-3-yl group; alternatively, a 2,4-disubstitutedpyridin-3-yl group or a 2,6-disubstituted pyridin-3-yl group;alternatively, a 2-substituted pyridin-3-yl group; alternatively, a4-substituted pyridin-3-yl group; alternatively, a 5-substitutedpyridin-3-yl group; alternatively, a 6-substituted pyridin-3-yl group;alternatively, a 2,4-disubstituted pyridin-3-yl group; alternatively, a2,6-disubstituted pyridin-3-yl group; or alternatively, a2,4,6-trisubstituted pyridin-3-yl group. In an embodiment, thesubstituted pyridinyl R³ group can be a 2-substituted pyridin-4-ylgroup, a 3-substituted pyridin-4-yl group, a 5-substituted pyridin-4-ylgroup, a 6-substituted pyridin-4-yl group, a 2,6-disubstitutedpyridin-4-yl group, or a 3,5-disubstituted pyridin-4-yl group;alternatively, a 2-substituted pyridin-4-yl group or a 6-substitutedpyridin-4-yl group; alternatively, a 3-substituted pyridin-4-yl group ora 5-substituted pyridin-4-yl group; alternatively, a 2-substitutedpyridin-4-yl group; alternatively, a 3-substituted pyridin-4-yl group;alternatively, a 5-substituted pyridin-4-yl group; alternatively, a6-substituted pyridin-4-yl group; alternatively, a 2,6-disubstitutedpyridin-4-yl group; or alternatively, a 3,5-disubstituted pyridin-4-ylgroup.

In an embodiment, the furyl (or substituted furyl) R³ group can be afur-2-yl group, a substituted fur-2-yl group, a fur-3-yl group, or asubstituted fur-3-yl group; alternatively, a fur-2-yl or a fur-3-ylgroup. In some embodiments, the furyl (or substituted furyl) R³ groupcan be a fur-2-yl group or a substituted fur-2-yl group; alternatively,a fur-3-yl group or a substituted fur-3-yl group; alternatively, afur-2-yl group; alternatively, a substituted fur-2-yl group;alternatively, a fur-3-yl group; or alternatively, a substitutedfur-3-yl group. In an embodiment, the substituted furyl R³ group can bea 2-substituted fur-3-yl group, a 4-substituted fur-3-yl group, or a2,4-disubstituted fur-3-yl group; alternatively, a 2-substitutedfur-3-yl group; alternatively, a 4-substituted fur-3-yl group; oralternatively, a 2,4-disubstituted fur-3-yl group.

In an embodiment, the thienyl (or substituted thienyl) R³ group can be athien-2-yl group, a substituted thien-2-yl group, a thien-3-yl group, ora substituted thien-3-yl group; alternatively, a thien-2-yl group or athien-3-yl group. In some embodiments, thienyl (or substituted thienyl)R³ group can be a thien-2-yl group or a substituted thien-2-yl group;alternatively, a thien-3-yl group or a substituted thien-3-yl group;alternatively, a thien-2-yl group; alternatively, a substitutedthien-2-yl group; alternatively, a thien-3-yl group; or alternatively, asubstituted thien-3-yl group. In an embodiment, the substituted thienylR³ group can be a 2-substituted thien-3-yl group, a 4-substitutedthien-3-yl group, or a 2,4-disubstituted thien-3-yl group;alternatively, a 2-substituted thien-3-yl group; alternatively, a4-substituted thien-3-yl group; or alternatively, a 2,4-disubstitutedthien-3-yl group.

In an embodiment, each substituent for a substituted pyridinyl, furyl,and/or thienyl groups (general or specific) that can be utilized as R³independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, each substituent for a substituted pyridinyl, furyl, and/orthienyl groups (general or specific) that can be utilized as R³independently can be a halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, a halogen oran alkoxy group; alternatively, an alkyl group or an alkoxy group;alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Halogens, hydrocarbyl groups,hydrocarboxy groups, alkyl groups, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for the substitutedpyridinyl, furyl, and/or thienyl groups (general or specific) that canbe utilized as R³.

General and specific non-hydrogen substituents of a substitutedcycloalkyl group (general or specific), a substituted aliphaticheterocyclic group (general or specific), a substituted cycloheterylgroup (general or specific), a substituted aromatic group (general orspecific), a substituted aryl group (general or specific), a substitutedheteroaryl group (general or specific), or a substituted arylheterylgroup (general or specific) are disclosed herein. These general andspecific non-hydrogen substituents can be utilized, without limitation,to further describe the substituted cycloalkyl groups (general orspecific), substituted aliphatic heterocyclic groups (general orspecific), substituted cycloheteryl groups (general or specific),substituted aromatic groups (general or specific), substituted arylgroups (general or specific), substituted heteroaryl groups (general orspecific), substituted arylheteryl group (general or specific), or anyother general or specific group which can be utilized as R³.

In a non-limiting embodiment, R³ can be a phenyl group, a 2-alkylphenylgroup, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenylgroup, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group;alternatively, a 2,4-dialkylphenyl group or a 2,6-dialkylphenyl group;alternatively, a 2,6-dialkylphenyl group, or a 2,4,6-trialkylphenylgroup; alternatively, a 3-alkylphenyl group or a 3,5-dialkylphenylgroup; alternatively, a 2-alkylphenyl group or a 2,6-dialkylphenylgroup; alternatively, a 2-alkylphenyl group; alternatively, a3-alkylphenyl group; alternatively, a 4-alkylphenyl group;alternatively, a 2,4-dialkylphenyl group; alternatively, a2,6-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group; oralternatively, a 2,4,6-trialkylphenyl group. In another non-limitingembodiment, R³ can be a phenyl group, a 2-alkoxyphenyl group, a3-alkoxyphenyl group, a 4-alkoxyphenyl group, or a 3,5-dialkoxyphenylgroup; alternatively, a 2-alkoxyphenyl group or a 4-alkoxyphenyl group;alternatively, a 3-alkoxyphenyl group or 3,5-dialkoxyphenyl group;alternatively, a 2-alkoxyphenyl group; alternatively, a 3-alkoxyphenylgroup; alternatively, a 4-alkoxyphenyl group; alternatively, a3,5-dialkoxyphenyl group. In other non-limiting embodiments, R¹ can be aphenyl group, a 2-halophenyl group, a 3-halophenyl group, a 4-halophenylgroup, a 2,6-dihalophenyl group, or a 3,5-dialkylphenyl group;alternatively, a 2-halophenyl group, a 4-halophenyl group, or a2,6-dihalophenyl group; alternatively, a 2-halophenyl group or a4-halophenyl group; alternatively, a 3-halophenyl group or a3,5-dihalophenyl group; alternatively, a 2-halophenyl group;alternatively, a 3-halophenyl group; alternatively, a 4-halophenylgroup; alternatively, a 2,6-dihalophenyl group; or alternatively, a3,5-dihalophenyl group. Halogens, alkyl groups, and alkoxy groups areindependently described herein (e.g. as substituents for substituted R¹groups) and can be utilized, without limitation, to further describe thealkylphenyl, dialkylphenyl, trialkylphenyl, alkoxyphenyl,dialkoxyphenyl, halophenyl, or dihalophenyl groups that can be utilizedR³. Generally, the halides, alkyl substituents, or alkoxy substituentsof a dialkyl, trialkyl phenyl, dialkoxyphenyl, or dihalophenyl group canbe the same; or alternatively, the halo, alkyl substituents, or alkoxysubstituents of alkylphenyl, dialkylphenyl, trialkylphenyl,dialkoxyphenyl, or dihalophenyl groups can be different.

In a non-limiting embodiment, R³ can be a 2-methylphenyl group, a2-ethylphenyl group, a 2-isopropylphenyl group, a 2-tert-butylphenylgroup, a 4-methylphenyl group, a 4-ethylphenyl group, a4-isopropylphenyl group, a 4-tert-butylphenyl group, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-diisopropylphenyl group, or a 2,6-di-tert-butylphenyl group;alternatively, a 2-methylphenyl group, a 2-ethylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group, a 4-methylphenylgroup, a 4-ethylphenyl group, a 4-isopropylphenyl group, or a4-tert-butylphenyl group; alternatively, a 2-methylphenyl group, a2-ethylphenyl group, a 2-isopropylphenyl group, or a 2-tert-butylphenylgroup; alternatively, a 4-methylphenyl group, a 4-ethylphenyl group, a4-isopropylphenyl group, or a 4-tert-butylphenyl group; oralternatively, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, or a2,6-di-tert-butylphenyl group. In another non-limiting embodiment, R³can be a 2-methylphenyl group; alternatively, a 2-ethylphenyl group;alternatively, a 2-isopropylphenyl group; alternatively, a2-tert-butylphenyl group; alternatively, a 4-methylphenyl group;alternatively, a 4-ethylphenyl group; alternatively, a 4-isopropylphenylgroup; or alternatively, a 4-tert-butylphenyl group.

In an aspect, R⁴ and/or R⁵ independently can be an organyl group, anorganyl group consisting essentially of inert functional groups, or ahydrocarbyl group. In an embodiment, R⁴ and/or R⁵ independently can be aC₁ to C₃₀ organyl group; alternatively, a C₁ to C₂₀ organyl group;alternatively, a C₁ to C₁₅ organyl group; alternatively, a C₁ to C₁₀organyl group; or alternatively, a C₁ to C₅ organyl group. In anembodiment, R⁴ and/or R⁵ independently can be a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups; alternatively, a C₁to C₂₀ organyl group consisting essentially of inert functional groups;alternatively, a C₁ to C₁₅ organyl group consisting essentially of inertfunctional groups; alternatively, a C₁ to C₁₀ organyl group consistingessentially of inert functional groups; or alternatively, a C₁ to C₅organyl group consisting essentially of inert functional groups. In anembodiment, R⁴ and/or R⁵ independently can be a C₁ to C₃₀ hydrocarbylgroup; alternatively, a C₁ to C₂₀ hydrocarbyl group; alternatively, a C₁to C₁₅ hydrocarbyl group; alternatively, a C₁ to C₁₀ hydrocarbyl group;or alternatively, a C₁ to C₅ hydrocarbyl group In yet other embodiments,R⁴ and R⁵ can be independently selected from a C₃ to C₃₀ aromatic group;alternatively, a C₃ to C₂₀ aromatic group; alternatively, a C₃ to C₁₅aromatic group; or alternatively, a C₃ to C₁₀ aromatic group. In anaspect, R⁴ and R⁵ can be joined to form a ring (regardless of particulartype of group—organyl, organyl consisting of inert functional groups,hydrocarbyl, or any species within) containing the phosphorus atom ofthe N²-phosphinyl amidine group.

In another aspect, R⁴ and/or R⁵ independently can be a C₁ to C₃₀ alkylgroup, a C₄ to C₃₀ cycloalkyl group, a C₄ to C₃₀ substituted cycloalkylgroup, a C₃ to C₃₀ aliphatic heterocyclic group, a C₃ to C₃₀ substitutedaliphatic heterocyclic group, a C₆ to C₃₀ aryl group, a C₆ to C₃₀substituted aryl group, a C₃ to C₃₀ heteroaryl group, or a C₃ to C₃₀substituted heteroaryl group; alternatively, a C₁ to C₃₀ alkyl group, aC₄ to C₃₀ cycloalkyl group, a C₄ to C₃₀ substituted cycloalkyl group, aC₆ to C₃₀ aryl group, or a C₆ to C₃₀ substituted aryl group;alternatively, a C₄ to C₃₀ cycloalkyl group or a C₄ to C₃₀ substitutedcycloalkyl group; alternatively, a C₃ to C₃₀ aliphatic heterocyclicgroup or a C₃ to C₃₀ substituted aliphatic heterocyclic group;alternatively, a C₆ to C₃₀ aryl group or a C₆ to C₃₀ substituted arylgroup; alternatively, a C₃ to C₃₀ heteroaryl group or a C₃ to C₃₀substituted heteroaryl group; alternatively, a C₁ to C₃₀ alkyl group;alternatively, a C₄ to C₃₀ cycloalkyl group; alternatively, a C₄ to C₃₀substituted cycloalkyl group; alternatively, a C₃ to C₃₀ aliphaticheterocyclic group; alternatively, a C₃ to C₃₀ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₃₀ aryl group;alternatively, a C₆ to C₃₀ substituted aryl group; alternatively, a C₃to C₃₀ heteroaryl group; or alternatively, a C₃ to C₃₀ substitutedheteroaryl group. In an embodiment, R⁴ and R⁵ independently can be a C₁to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀substituted cycloalkyl group, a C₃ to C₂₀ aliphatic heterocyclic group,a C₃ to C₂₀ substituted aliphatic heterocyclic group, a C₆ to C₂₀ arylgroup, a C₆ to C₂₀ substituted aryl group, a C₃ to C₂₀ heteroaryl group,or a C₃ to C₂₀ substituted heteroaryl group; alternatively, a C₁ to C₁₅alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substitutedcycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆ to C₂₀ substitutedaryl group; alternatively, a C₄ to C₂₀ cycloalkyl group or a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₃ to C₂₀ aliphaticheterocyclic group or a C₃ to C₂₀ substituted aliphatic heterocyclicgroup; alternatively, a C₆ to C₂₀ aryl group or a C₆ to C₂₀ substitutedaryl group; alternatively, a C₃ to C₂₀ heteroaryl group or a C₃ to C₂₀substituted heteroaryl group; alternatively, a C₁ to C₁₅ alkyl group;alternatively, a C₄ to C₂₀ cycloalkyl group; alternatively, a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₃ to C₂₀ aliphaticheterocyclic group; alternatively, a C₃ to C₂₀ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₂₀ aryl group;alternatively, a C₆ to C₂₀ substituted aryl group; alternatively, a C₃to C₂₀ heteroaryl group; or alternatively, a C₃ to C₂₀ substitutedheteroaryl group. In other embodiments, R⁴ and R⁵ independently can be aC₁ to C₁₀ alkyl group, a C₄ to C₁₅ cycloalkyl group, a C₄ to C₁₅substituted cycloalkyl group, a C₃ to C₁₅ aliphatic heterocyclic group,a C₃ to C₁₅ substituted aliphatic heterocyclic group, a C₆ to C₁₅ arylgroup, a C₆ to C₁₅ substituted aryl group, a C₃ to C₁₅ heteroaryl group,or a C₃ to C₁₅ substituted heteroaryl group; alternatively, a C₁ to C₁₀alkyl group, a C₄ to C₁₅ cycloalkyl group, a C₄ to C₁₅ substitutedcycloalkyl group, a C₆ to C₁₅ aryl group, or a C₆ to C₁₅ substitutedaryl group; alternatively, a C₄ to C₁₅ cycloalkyl group or a C₄ to C₁₅substituted cycloalkyl group; alternatively, a C₃ to C₁₅ aliphaticheterocyclic group or a C₃ to C₁₅ substituted aliphatic heterocyclicgroup; alternatively, a C₆ to C₁₅ aryl group or a C₆ to C₁₅ substitutedaryl group; alternatively, a C₃ to C₁₅ heteroaryl group or a C₃ to C₁₅substituted heteroaryl group; alternatively, a C₁ to C₁₀ alkyl group;alternatively, a C₄ to C₁₅ cycloalkyl group; alternatively, a C₄ to C₁₅substituted cycloalkyl group; alternatively, a C₃ to C₁₅ aliphaticheterocyclic group; alternatively, a C₃ to C₁₅ substituted aliphaticheterocyclic group; alternatively, a C₆ to C₁₅ aryl group;alternatively, a C₆ to C₁₅ substituted aryl group; alternatively, a C₃to C₁₅ heteroaryl group; or alternatively, a C₃ to C₁₅ substitutedheteroaryl group. In further embodiments, R⁴ and R⁵ independently can beC₁ to C₅ alkyl group.

In a further aspect, R⁴ and/or R⁵ independently can be a methyl group,an ethyl group, a propyl group, a butyl group, a pentyl group, a hexylgroup, a heptyl group, an octyl group, a nonyl group, a decyl group, aundecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, apentadecyl group, a hexadecyl group, a heptadecyl group, an octadecylgroup, or a nonadecyl group; or alternatively, a methyl group, an ethylgroup, a propyl group, a butyl group, a pentyl group, a hexyl group, aheptyl group, an octyl group, a nonyl group, or a decyl group. In someembodiments, R⁴ and R⁵ independently can be a methyl group, an ethylgroup, an n-propyl group, an iso-propyl group, an n-butyl group, aniso-butyl group, a sec-butyl group, a tert-butyl group, an n-pentylgroup, an iso-pentyl group, a sec-pentyl group, or a neopentyl group;alternatively, a methyl group, an ethyl group, an iso-propyl group, atert-butyl group, or a neopentyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an n-propyl group;alternatively, an iso-propyl group; alternatively, a tert-butyl group;or alternatively, a neopentyl group. In some embodiments, the alkylgroups which can be utilized as R⁴ and/or R⁵ can be substituted. Eachsubstituent of a substituted alkyl group independently can be a halogenor a hydrocarboxy group; alternatively, a halogen; or alternatively, ahydrocarboxy group. Halogens, hydrocarbyl groups, hydrocarboxy groups,alkyl groups, and alkoxy groups that can be utilized as substituents areindependently disclosed herein (e.g. as substituents for substituted R¹groups) and can be utilized without limitation to further describe thesubstituted alkyl group which can be utilized as R⁴ and/or R⁵.

In a further aspect, R⁴ and/or R⁵ independently can be a cyclobutylgroup, a substituted cyclobutyl group, a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, a substitutedcyclohexyl group, a cycloheptyl group, a substituted cycloheptyl group,a cyclooctyl group, or a substituted cyclooctyl group. In someembodiments, R⁴ and R⁵ independently can be a cyclopentyl group, asubstituted cyclopentyl group, a cyclohexyl group, or a substitutedcyclohexyl group. In other embodiments, R⁴ and R⁵ may be a cyclobutylgroup or a substituted cyclobutyl group; alternatively, a cyclopentylgroup or a substituted cyclopentyl group; alternatively, a cyclohexylgroup or a substituted cyclohexyl group; alternatively, a cycloheptylgroup or a substituted cycloheptyl group; or alternatively, a cyclooctylgroup or a substituted cyclooctyl group. In further embodiments, R⁴ andR⁵ independently can be a cyclopentyl group; alternatively, asubstituted cyclopentyl group; a cyclohexyl group; or alternatively, asubstituted cyclohexyl group.

In an embodiment, each substituent for a substituted cycloalkyl group(general or specific) that can be utilized as R⁴ and/or R⁵ independentlycan be a halogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, each substituent for a substituted cycloalkyl group(general or specific) that can be utilized as R⁴ and/or R⁵ independentlycan be a halogen, an alkyl group, or an alkoxy group; alternatively, ahalogen or an alkyl group; alternatively, a halogen or an alkoxy group;alternatively, an alkyl group or an alkoxy group; alternatively, ahalogen; alternatively, an alkyl group; or alternatively, an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein (e.g. as substituents for substituted R¹ groups) andcan be utilized without limitation to further describe the substituentsfor a substituted cycloalkyl group (general or specific) that can beutilized as R⁴ and/or R⁵.

In an aspect, R⁴ can have Structure G7:

wherein, the undesignated valency is attached to the phosphorus atom ofthe N²-phosphinylamidine group. Generally, R^(41c), R^(42c), R^(43c),R^(44c), and R^(45c) independently can be hydrogen or a non-hydrogensubstituent, and n can be an integer from 1 to 5. In an embodimentwherein R⁴ has Structure G7, R^(41c), R^(43c), R^(44c), and R^(45c) canbe hydrogen and R^(32c) can be any non-hydrogen substituent disclosedherein; or alternatively, R^(41c), R^(43c), and R^(45c) can be hydrogenand R^(42c) and R^(44c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively, 3.

In an embodiment, R^(41c), R^(42c), R^(43c), R^(44c), and R^(45c)independently can be hydrogen, a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, hydrogen, a halogen, or a hydrocarbylgroup; alternatively, hydrogen, a halogen, or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, hydrogen or a halogen; alternatively, hydrogen or ahydrocarbyl group; or alternatively, hydrogen or a hydrocarboxy group.In some embodiments, R^(41c), R^(42c), R^(43c), R^(44c), and R^(45c)independently can be hydrogen, a halogen, an alkyl group, or an alkoxygroup; alternatively, hydrogen, a halogen, or an alkyl group;alternatively, hydrogen, a halogen, an alkyl group, or an alkoxy group;alternatively, hydrogen, an alkyl group, or an alkoxy group;alternatively, hydrogen or a halogen; alternatively, hydrogen or analkyl group; or alternatively, hydrogen or an alkoxy group. Halogens,hydrocarbyl groups, hydrocarboxy groups, alkyl groups, and alkoxy groupsthat can be utilized as substituents are independently disclosed herein(e.g. as substituents for substituted R¹ groups) and can be utilizedwithout limitation to further describe the R⁴ group having Structure G7.

In an aspect, R⁵ can have Structure G8:

wherein, the undesignated valency is attached to the phosphorus atom ofthe N²-phosphinylamidine group. Generally, R^(51c), R^(52c), R^(53c),R^(54c), and R^(55c) independently can be hydrogen or a non-hydrogensubstituent, and n may be an integer from 1 to 5. In an embodimentwherein R⁵ has Structure G8, R^(51c), R^(53c), R^(54c), and R^(55c) canbe hydrogen and R^(32c) can be any non-hydrogen substituent disclosedherein; or alternatively, R^(51c), R^(53c), and R^(55c) can be hydrogenand R^(52c) and R^(54c) independently can be any non-hydrogensubstituent disclosed herein. In an embodiment, n can be an integer from1 to 4; or alternatively, from 2 to 4. In other embodiments, n can be 2or 3; alternatively, 2; or alternatively, 3.

In an embodiment, R^(51c), R^(52c), R^(53c), R^(54c), and R^(55c)independently can be hydrogen, a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, hydrogen, a halogen, or a hydrocarbylgroup; alternatively, hydrogen, a halogen, or a hydrocarboxy group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, hydrogen or a halogen; alternatively, hydrogen or ahydrocarbyl group; or alternatively, hydrogen or a hydrocarboxy group.In some embodiments, R^(51c), R^(52c), R^(53c), R^(54c), and R^(55c)independently can be hydrogen, a halogen, an alkyl group, or an alkoxygroup; alternatively, hydrogen, a halogen, or an alkyl group;alternatively, hydrogen, a halogen, or an alkoxy group; alternatively,hydrogen, an alkyl group, or an alkoxy group; alternatively, hydrogen ora halogen; alternatively, hydrogen or an alkyl group; or alternatively,hydrogen or an alkoxy group. Halogens, hydrocarbyl groups, hydrocarboxygroups, alkyl groups, and alkoxy groups that can be utilized assubstituents are independently disclosed herein (e.g. as substituentsfor substituted R¹ groups) and can be utilized without limitation tofurther describe the R⁵ group having Structure G8.

In an aspect, R⁴ and/or R⁵ independently can be a phenyl group, asubstituted phenyl group, a naphthyl group, or a substituted naphthylgroup. In an embodiment, R⁴ and R⁵ independently can be a phenyl groupor a substituted phenyl group; alternatively, a naphthyl group or asubstituted naphthyl group; alternatively, a phenyl group or a naphthylgroup; or alternatively, a substituted phenyl group or a substitutednaphthyl group. In some embodiments, R⁴ and/or R⁵ independently can be aphenyl group; alternatively, a substituted phenyl group; alternatively,a naphthyl group; or alternatively, a substituted naphthyl group.

In an embodiment, the R⁴ and/or R⁵ substituted phenyl group can be a2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other embodiments, the R⁴ and/orR⁵ substituted phenyl group can be a 2-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group;alternatively, a 2-substituted phenyl group, a 4-substituted phenylgroup, a 2,4-disubstituted phenyl group, or a 2,6-disubstituted phenylgroup; alternatively, a 3-substituted phenyl group or a3,5-disubstituted phenyl group; alternatively, a 2-substituted phenylgroup or a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group or a 2,4,6-trisubstituted phenyl group; alternatively, a2,4-disubstituted phenyl group or a 2,6-disubstituted phenyl group;alternatively, a 2-substituted phenyl group; alternatively, a3-substituted phenyl group; alternatively, a 4-substituted phenyl group;alternatively, a 2,4-disubstituted phenyl group; alternatively, a2,6-disubstituted phenyl group; alternatively, a 3,5-disubstitutedphenyl group; or alternatively, a 2,4,6-trisubstituted phenyl group.

In an embodiment, R⁴ and/or R⁵ independently can be a naphth-1-yl group,a substituted naphth-1-yl group, a naphth-2-yl group, or a substitutednaphth-2-yl group. In some embodiments, R⁴ and/or R⁵ independently canbe a naphth-1-yl group or a substituted naphth-1-yl group;alternatively, a naphth-2-yl group or a substituted naphth-2-yl group;alternatively, a naphth-1-yl group; alternatively, a substitutednaphth-1-yl group; alternatively, a naphth-2-yl group; or alternatively,a substituted naphth-2-yl group. In other embodiments, R⁴ and/or R⁵independently can be a 2-substituted naphth-1-yl group, a 3-substitutednaphth-1-yl group, a 4-substituted naphth-1-yl group, or a 8-substitutednaphth-1-yl group; alternatively, a 2-substituted naphth-1-yl group;alternatively, a 3-substituted naphth-1-yl group; alternatively, a4-substituted naphth-1-yl group; or alternatively, a 8-substitutednaphth-1-yl group. In further embodiments, R⁴ and/or R⁵ independentlycan be a 1-substituted naphth-2-yl group, a 3-substituted naphth-2-ylgroup, a 4-substituted naphth-2-yl group, or a 1,3-disubstitutednaphth-2-yl group; alternatively, a 1-substituted naphth-2-yl group;alternatively, a 3-substituted naphth-2-yl group; alternatively, a4-substituted naphth-2-yl group; alternatively, a 1,3-disubstitutednaphth-2-yl group.

In an embodiment, each substituent for a substituted phenyl orsubstituted naphthyl R⁴ and/or R⁵ group independently can be a halogen,a hydrocarbyl group, or a hydrocarboxy group; alternatively, a halogenor a hydrocarbyl group; alternatively, a halogen or a hydrocarboxygroup; alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituent for a substituted phenyl or substituted naphthyl R⁴ and/orR⁵ group independently can be a halogen, an alkyl group, or an alkoxygroup; alternatively, a halogen or an alkyl group; alternatively, ahalogen or an alkoxy group; alternatively, an alkyl group or an alkoxygroup; alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Halogens, hydrocarbyl groups,hydrocarboxy groups, alkyl groups, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for the substitutedphenyl or substituted naphthyl R⁴ and/or R⁵ group.

In an aspect, R⁴ have Structure G9:

wherein the undesignated valency is attached to the phosphorus atom ofthe N²-phosphinyl amidine group. Generally, R⁴², R⁴³, R⁴⁴, R⁴⁵, R⁴⁶ canindependently be hydrogen or a non-hydrogen substituent. In anembodiment wherein R⁴ has Structure G9, R⁴², R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ canbe hydrogen, R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴² can be anon-hydrogen substituent, R⁴², R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴³can be a non-hydrogen substituent, R⁴², R⁴³, R⁴⁵, and R⁴⁶ can behydrogen and R⁴⁴ can be a non-hydrogen substituent, R⁴³, R⁴⁵, and R⁴⁶can be hydrogen and R⁴² and R⁴⁴ can be non-hydrogen substituents, R⁴³,R⁴⁴, and R⁴⁵ can be hydrogen and R⁴² and R⁴⁶ can be non-hydrogensubstituents, R⁴², R⁴⁴, and R⁴⁶ can be hydrogen and R⁴³ and R⁴⁵ can benon-hydrogen substituents, or R⁴³ and R⁴⁵ can be hydrogen and R⁴², R⁴⁴,and R⁴⁶ can be non-hydrogen substituents. In some embodiments wherein R⁴has Structure G9, R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴² can bea non-hydrogen substituent, R⁴², R⁴³, R⁴⁵, and R⁴⁶ can be hydrogen andR⁴⁴ can be a non-hydrogen substituent, R⁴³, R⁴⁵, and R⁴⁶ can be hydrogenand R⁴² and R⁴⁴ can be non-hydrogen substituents, R⁴³, R⁴⁴, and R⁴⁵ canbe hydrogen and R⁴² and R⁴⁶ can be non-hydrogen substituents, or R⁴³ andR⁴⁵ can be hydrogen and R⁴², R⁴⁴, and R⁴⁶ can be non-hydrogensubstituents; alternatively, R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen andR⁴² can be a non-hydrogen substituent, R⁴², R⁴³, R⁴⁵, and R⁴⁶ can behydrogen and R⁴⁴ can be a non-hydrogen substituent, R⁴³, R⁴⁵, and R⁴⁶can be hydrogen and R⁴² and R⁴⁴ can be non-hydrogen substituents, orR⁴³, R⁴⁴, and R⁴⁵ can be hydrogen and R⁴² and R⁴⁶ can be non-hydrogensubstituents; alternatively, R⁴², R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen andR⁴³ can be a non-hydrogen substituent, or R⁴², R⁴⁴, and R⁴⁶ can behydrogen and R⁴³ and R⁴⁵ can be non-hydrogen substituents;alternatively, R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴² can be anon-hydrogen substituent, or R⁴², R⁴³, R⁴⁵, and R⁴⁶ can be hydrogen andR⁴⁴ can be a non-hydrogen substituent; alternatively, R⁴³, R⁴⁵, and R⁴⁶can be hydrogen and R⁴² and R⁴⁴ can be non-hydrogen substituents, R⁴³,R⁴⁴, and R⁴⁵ can be hydrogen and R⁴² and R⁴⁶ can be non-hydrogensubstituents, or R⁴³ and R⁴⁵ can be hydrogen and R⁴², R⁴⁴, and R⁴⁶ canbe non-hydrogen substituents; or alternatively, R⁴³, R⁴⁵, and R⁴⁶ can behydrogen and R⁴² and R⁴⁴ can be non-hydrogen substituents, or R⁴³, R⁴⁴,and R⁴⁵ can be hydrogen and R⁴² and R⁴⁶ can be non-hydrogensubstituents. In other embodiments wherein R⁴ has Structure G9, R⁴²,R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen; alternatively, R⁴³, R⁴⁴, R⁴⁵,and R⁴⁶ can be hydrogen and R⁴² can be a non-hydrogen substituent;alternatively, R⁴², R⁴⁴, R⁴⁵, and R⁴⁶ can be hydrogen and R⁴³ can be anon-hydrogen substituent; alternatively, R⁴², R⁴³, R⁴⁵, and R⁴⁶ can behydrogen and R⁴⁴ can be a non-hydrogen substituent; alternatively, R⁴³,R⁴⁵, and R⁴⁶ can be hydrogen and R⁴² and R⁴⁴ can be non-hydrogensubstituents; alternatively, R⁴³, R⁴⁴, and R⁴⁵ can be hydrogen and R⁴²and R⁴⁶ can be non-hydrogen substituents; alternatively, R⁴², R⁴⁴, andR⁴⁶ can be hydrogen and R⁴³ and R⁴⁵ and can be non-hydrogensubstituents; or alternatively, R⁴³ and R⁴⁵ can be hydrogen and R⁴²,R⁴⁴, and R⁴⁶ can be non-hydrogen substituents.

In an embodiment, the non-hydrogen substituents that can be utilized asR⁴², R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ in the R¹ group having Structure G9independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen, or a hydrocarbyl group; alternatively,halogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, the non-hydrogen substituents that can be utilized as R⁴²,R⁴³, R⁴⁴, R⁴⁵, and R⁴⁶ in the R¹ group having Structure G9 independentlycan be a halogen, an alkyl group, or an alkoxy group; alternatively, ahalogen, or an alkyl group; alternatively, a halogen or an alkoxy group;alternatively, an alkyl group or an alkoxy group; alternatively, ahalogen; alternatively, an alkyl group; or alternatively, an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein (e.g. as substituents for substituted R¹ groups) andcan be utilized without limitation to further describe the R⁴ grouphaving Structure G9.

In an aspect, R⁵ can have Structure G10:

wherein the undesignated valency is attached to the phosphorus atom ofthe N²-phosphinyl amidine group. Generally, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶independently can be hydrogen or a non-hydrogen substituent. In anembodiment wherein R⁵ has Structure G10, R⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ canbe hydrogen, R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵² can be anon-hydrogen substituent, R⁵², R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵³can be a non-hydrogen substituent, R⁵², R⁵³, R⁵⁵, and R⁵⁶ can behydrogen and R⁵⁴ can be a non-hydrogen substituent, R⁵³, R⁵⁵, and R⁵⁶can be hydrogen and R⁵² and R⁵⁴ can be non-hydrogen substituents, R⁵³,R⁵⁴, and R⁵⁵ can be hydrogen and R⁵² and R⁵⁶ can be non-hydrogensubstituents, R⁵², R⁵⁴, and R⁵⁶ can be hydrogen and R⁵³ and R⁵⁵ can benon-hydrogen substituents, or R⁵³ and R⁵⁵ can be hydrogen and R⁵², R⁵⁴,and R⁵⁶ can be non-hydrogen substituents. In some embodiments wherein R⁵has Structure G10, R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵² can bea non-hydrogen substituent, R⁵², R⁵³, R⁵⁵, and R⁵⁶ can be hydrogen andR⁵⁴ can be a non-hydrogen substituent, R⁵³, R⁵⁵, and R⁵⁶ can be hydrogenand R⁵² and R⁵⁴ can be non-hydrogen substituents, R⁵³, R⁵⁴, and R⁵⁵ canbe hydrogen and R⁵² and R⁵⁶ can be non-hydrogen substituents, or R⁵³ andR⁵⁵ can be hydrogen and R⁵², R⁵⁴, and R⁵⁶ can be non-hydrogensubstituents; alternatively, R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen andR⁵² can be a non-hydrogen substituent, R⁵², R⁵³, R⁵⁵, and R⁵⁶ can behydrogen and R⁵⁴ can be a non-hydrogen substituent, R⁵³, R⁵⁵, and R⁵⁶can be hydrogen and R⁵² and R⁵⁴ can be non-hydrogen substituents, orR⁵³, R⁵⁴, and R⁵⁵ can be hydrogen and R⁵² and R⁵⁶ can be non-hydrogensubstituents; alternatively, R⁵², R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen andR⁵³ can be a non-hydrogen substituent, or R⁵², R⁵⁴, and R⁵⁶ can behydrogen and R⁵³ and R⁵⁵ can be non-hydrogen substituents;alternatively, R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵² can be anon-hydrogen substituent, or R⁵², R⁵³, R⁵⁵, and R⁵⁶ can be hydrogen andR⁵⁴ can be a non-hydrogen substituent; alternatively, R⁵³, R⁵⁵, and R⁵⁶can be hydrogen and R⁵² and R⁵⁴ can be non-hydrogen substituents, R⁵³,R⁵⁴, and R⁵⁵ can be hydrogen and R⁵² and R⁵⁶ can be non-hydrogensubstituents, or R⁵³ and R⁵⁵ can be hydrogen and R⁵², R⁵⁴, and R⁵⁶ canbe non-hydrogen substituents; or alternatively, R⁵³, R⁵⁵, and R⁵⁶ can behydrogen and R⁵² and R⁵⁴ can be non-hydrogen substituents, or R⁵³, R⁵⁴,and R⁵⁵ can be hydrogen and R⁵² and R⁵⁶ can be non-hydrogensubstituents. In other embodiments wherein R⁵ has Structure G10, R⁵²,R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen; alternatively, R⁵³, R⁵⁴, R⁵⁵,and R⁵⁶ can be hydrogen and R⁵² can be a non-hydrogen substituent;alternatively, R⁵², R⁵⁴, R⁵⁵, and R⁵⁶ can be hydrogen and R⁵³ can be anon-hydrogen substituent; alternatively, R⁵², R⁵³, R⁵⁵, and R⁵⁶ can behydrogen and R⁵⁴ can be a non-hydrogen substituent; alternatively, R⁵³,R⁵⁵, and R⁵⁶ can be hydrogen and R⁵² and R⁵⁴ can be non-hydrogensubstituents; alternatively, R⁵³, R⁵⁴, and R⁵⁵ can be hydrogen and R⁵²and R⁵⁶ can be non-hydrogen substituents; alternatively, R⁵², R⁵⁴, andR⁵⁶ can be hydrogen and R⁵³ and R⁵⁵ and can be non-hydrogensubstituents; or alternatively, R⁵³ and R⁵⁵ can be hydrogen and R⁵²,R⁵⁴, and R⁵⁶ can be non-hydrogen substituents.

In an embodiment, the non-hydrogen substituents that can be utilized asR⁵², R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ in the R⁵ group having Structure G2independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen, or a hydrocarboxy group; alternatively, a hydrocarbyl group ora hydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, the non-hydrogen substituents that can be utilized as R⁵²,R⁵³, R⁵⁴, R⁵⁵, and R⁵⁶ in the R⁵ group having Structure G2 independentlycan be a halogen, an alkyl group, or an alkoxy group; alternatively, ahalogen or an alkyl group; alternatively, a halogen or an alkoxy group;alternatively, an alkyl group or an alkoxy group; alternatively, ahalogen; alternatively, an alkyl group; or alternatively, an alkoxygroup. Halogens, hydrocarbyl groups, hydrocarboxy groups, alkyl groups,and alkoxy groups that can be utilized as substituents are independentlydisclosed herein (e.g. as substituents for substituted R¹ groups) andcan be utilized without limitation to further describe the R⁵ grouphaving Structure G10.

In an aspect, R⁴ and R⁵ independently can be a pyridinyl group, asubstituted pyridinyl group, a furyl group, a substituted furyl group, athienyl group, or a substituted thienyl group. In an embodiment, R⁴ andR⁵ independently can be a pyridinyl group or a substituted pyridinylgroup; alternatively, a furyl group or a substituted furyl group; oralternatively, a thienyl group or a substituted thienyl group. In someembodiments, R⁴ and R⁵ independently can be a pyridinyl group, a furylgroup, or a thienyl group. In other embodiments, R⁴ and R⁵ can be apyridinyl group; alternatively, a substituted pyridinyl group;alternatively, a furyl group; alternatively, a substituted furyl group;alternatively, a thienyl group; or alternatively, a substituted thienylgroup.

In an embodiment, the pyridinyl (or substituted pyridinyl) R⁴ and/or R⁵group independently can be a pyridin-2-yl group, a substitutedpyridin-2-yl group, a pyridin-3-yl group, a substituted pyridin-3-ylgroup, a pyridin-4-yl group, or a substituted pyridin-4-yl group;alternatively, a pyridin-2-yl group, a pyridin-3-yl group, or apyridin-4-yl group. In some embodiments, the pyridinyl (or substitutedpyridinyl) R⁴ and/or R⁵ group independently can be a pyridin-2-yl groupor a substituted pyridin-2-yl group; alternatively, a pyridin-3-yl groupor a substituted pyridin-3-yl group; alternatively, a pyridin-4-yl groupor a substituted pyridin-4-yl group; alternatively, a pyridin-2-ylgroup; alternatively, a substituted pyridin-2-yl group; alternatively, apyridin-3-yl group; alternatively, a substituted pyridin-3-yl group;alternatively, a pyridin-4-yl group; or alternatively, a substitutedpyridin-4-yl group. In an embodiment, the substituted pyridinyl R⁴and/or R⁵ group independently can be a 2-substituted pyridin-3-yl group,a 4-substituted pyridin-3-yl group, a 5-substituted pyridin-3-yl group,a 6-substituted pyridin-3-yl group, a 2,4-disubstituted pyridin-3-ylgroup, a 2,6-disubstituted pyridin-3-yl group, or a 2,4,6-trisubstitutedpyridin-3-yl group; alternatively, 2-substituted pyridin-3-yl group, a4-substituted pyridin-3-yl group, or a 6-substituted pyridin-3-yl group;alternatively, a 2,4-disubstituted pyridin-3-yl group or a2,6-disubstituted pyridin-3-yl group; alternatively, a 2-substitutedpyridin-3-yl group; alternatively, a 4-substituted pyridin-3-yl group;alternatively, a 5-substituted pyridin-3-yl group; alternatively, a6-substituted pyridin-3-yl group; alternatively, a 2,4-disubstitutedpyridin-3-yl group; alternatively, a 2,6-disubstituted pyridin-3-ylgroup; or alternatively, a 2,4,6-trisubstituted pyridin-3-yl group. Inan embodiment, the substituted pyridinyl R⁴ and/or R⁵ groupindependently can be a 2-substituted pyridin-4-yl group, a 3-substitutedpyridin-4-yl group, a 5-substituted pyridin-4-yl group, a 6-substitutedpyridin-4-yl group, a 2,6-disubstituted pyridin-4-yl group, or a3,5-disubstituted pyridin-4-yl group; alternatively, 2-substitutedpyridin-4-yl group or a 6-substituted pyridin-4-yl group; alternatively,a 3-substituted pyridin-4-yl group or a 5-substituted pyridin-4-ylgroup; alternatively, a 2-substituted pyridin-4-yl group; alternatively,a 3-substituted pyridin-4-yl group; alternatively, a 5-substitutedpyridin-4-yl group; alternatively, a 6-substituted pyridin-4-yl group;alternatively, a 2,6-disubstituted pyridin-4-yl group; or alternatively,a 3,5-disubstituted pyridin-4-yl group.

In an embodiment, each furyl (or substituted furyl) R⁴ and/or R⁵ groupcan be independently selected from a fur-2-yl group, a substitutedfur-2-yl group, a fur-3-yl group, or a substituted fur-3-yl group;alternatively, a fur-2-yl or a fur-3-yl group. In some embodiments, thefuryl (or substituted furyl) R⁴ and/or R⁵ group can be independentlyselected from a fur-2-yl group or a substituted fur-2-yl group;alternatively, a fur-3-yl group or a substituted fur-3-yl group;alternatively, a fur-2-yl group; alternatively, a substituted fur-2-ylgroup; alternatively, a fur-3-yl group; or alternatively, a substitutedfur-3-yl group. In an embodiment, the substituted furyl R⁴ and/or R⁵group can be a 2-substituted fur-3-yl group, a 4-substituted fur-3-ylgroup, or a 2,4-disubstituted fur-3-yl group; alternatively, a2-substituted fur-3-yl group; alternatively, a 4-substituted fur-3-ylgroup; or alternatively, a 2,4-disubstituted fur-3-yl group.

In an embodiment, the thienyl (or substituted thienyl) R⁴ and/or R⁵group can be independently selected from a thien-2-yl group, asubstituted thien-2-yl group, a thien-3-yl group, or a substitutedthien-3-yl group; alternatively, a thien-2-yl group or a thien-3-ylgroup. In some embodiments, the thienyl (or substituted thienyl) R⁴and/or R⁵ group can be independently selected from a thien-2-yl group ora substituted thien-2-yl group; alternatively, a thien-3-yl group or asubstituted thien-3-yl group; alternatively, a thien-2-yl group;alternatively, a substituted thien-2-yl group; alternatively, athien-3-yl group; or alternatively, a substituted thien-3-yl group. Inan embodiment, the substituted thienyl R⁴ and/or R⁵ group can be a2-substituted thien-3-yl group, a 4-substituted thien-3-yl group, or a2,4-disubstituted thien-3-yl group; alternatively, a 2-substitutedthien-3-yl group; alternatively, a 4-substituted thien-3-yl group; oralternatively, a 2,4-disubstituted thien-3-yl group.

In an embodiment, substituent for a substituted pyridinyl, furyl, and/orthienyl group (general or specific) that can be utilized as R⁴ and/or R⁵independently can be a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, a halogen or a hydrocarbyl group; alternatively, ahalogen or a hydrocarboxy group; alternatively, a hydrocarbyl group or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. In someembodiments, each substituent for a substituted pyridinyl, furyl, and/orthienyl groups (general or specific) that can be utilized as R⁴ and/orR⁵ independently can be a halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, a halogen oran alkoxy group; alternatively, an alkyl group or an alkoxy group;alternatively, a halogen; alternatively, an alkyl group; oralternatively, an alkoxy group. Halogens, hydrocarbyl groups,hydrocarboxy groups, alkyl groups, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for the substitutedpyridinyl, furyl, and/or thienyl groups (general or specific) can beutilized as R⁴ and/or R⁵.

General and specific non-hydrogen substituents of a substitutedcycloalkyl group (general or specific), a substituted aliphaticheterocyclic group (general or specific), a substituted cycloheterylgroup (general or specific), a substituted aromatic group (general orspecific), a substituted aryl group (general or specific), a substitutedheteroaryl group (general or specific), or a substituted arylheterylgroup (general or specific) are disclosed herein. These general andspecific non-hydrogen substituents can be utilized, without limitation,to further describe the substituted cycloalkyl groups (general orspecific), substituted aliphatic heterocyclic groups (general orspecific), substituted cycloheteryl groups (general or specific),substituted aromatic groups (general or specific), substituted arylgroups (general or specific), substituted heteroaryl groups (general orspecific), substituted arylheteryl group (general or specific), or anyother general or specific group which can be utilized as R⁴ and/or R⁵.

In an aspect, when R⁴ and R⁵ are joined to form a cyclic group includingthe phosphorus atom of the N²-phosphinyl amidine group, the phosphinylgroup can be a phosphol-1-yl group, a substituted phosphol-1-yl group, a2,3-dihydrophosphol-1-yl group, a substituted 2,3-dihydrophosphol-1-ylgroup, a 3,5-dihydrophosphol-1-yl group, a substituted3,5-dihydrophosphol-1-yl group, a phospholan-1-yl group, a substitutedphospholan-1-yl group, a 1,2-dihydrophosphinin-1-yl group, asubstituted, 1,2-dihydro-phosphinin-1-yl group, a1,4-dihydrophosphinin-1-yl group, a substituted1,4-dihydrophosphinin-1-yl group, a 1,2,3,4-tetrahydrophosphinin-1-ylgroup, a substituted 1,2,3,4-tetrahydrophosphinin-1-yl group, a1,2,3,6-tetrahydrophosphinin-1-yl group, a substituted1,2,3,6-tetrahydrophosphinin-1-yl group, a phosphinan-1-yl group, or asubstituted phosphinan-1-yl group. In some embodiments, when R⁴ and R⁵are joined to form a cyclic group including the phosphorus atom of theN²-phosphinylamidine group, the phosphinyl group can be a phosphol-1-ylgroup or a substituted phosphol-1-yl group; alternatively, a2,3-dihydrophosphol-1-yl group or a substituted 2,3-dihydrophosphol-1-ylgroup; alternatively, a 3,5-dihydrophosphol-1-yl group or a substituted3,5-dihydrophosphol-1-yl group; alternatively, a phospholan-1-yl groupor a substituted phospholan-1-yl group; alternatively, a1,2-dihydro-phosphinin-1-yl group or a substituted,1,2-dihydrophosphinin-1-yl group; alternatively, a1,4-dihydro-phosphinin-1-yl group or a substituted1,4-dihydrophosphinin-1-yl group; alternatively, a1,2,3,4-tetra-hydrophosphinin-1-yl group or a substituted1,2,3,4-tetrahydrophosphinin-1-yl group; alternatively, a1,2,3,6-tetrahydrophosphinin-1-yl group or a substituted1,2,3,6-tetrahydrophosphinin-1-yl group; or alternatively, aphosphinan-1-yl group or a substituted phosphinan-1-yl group. In someembodiments, when R⁴ and R⁵ are joined to form a cyclic group includingthe phosphorus atom of the N²-phosphinyl amidine group, the phosphinylgroup can be a phosphol-1-yl group, a 2,3-dihydrophosphol-1-yl group, a3,5-dihydrophosphol-1-yl group, a phospholan-1-yl group, a1,2-dihydrophosphinin-1-yl group, a 1,4-dihydrophosphinin-1-yl group, a1,2,3,4-tetrahydrophosphinin-1-yl group, a1,2,3,6-tetrahydrophosphinin-1-yl group, or a phosphinan-1-yl group. Inother embodiments, when R⁴ and R⁵ are joined to form a cyclic groupincluding the phosphorus atom of the N²-phosphinylamidine group, thephosphinyl group can be a substituted phosphol-1-yl group, a substituted2,3-dihydrophosphol-1-yl group, a substituted 3,5-dihydrophosphol-1-ylgroup, a substituted phospholan-1-yl group, a substituted,1,2-dihydrophosphinin-1-yl group, a substituted1,4-dihydro-phosphinin-1-yl group, a substituted1,2,3,4-tetrahydrophosphinin-1-yl group, a substituted1,2,3,6-tetra-hydrophosphinin-1-yl group, or a substitutedphosphinan-1-yl group. In yet other embodiments, a phospholan-1-ylgroup, a substituted phospholan-1-yl group, a phosphinan-1-yl group, ora substituted phosphinan-1-yl group; alternatively, a phospholan-1-ylgroup or a phosphinan-1-yl group; or alternatively, a substitutedphospholan-1-yl group or a substituted phosphinan-1-yl group. In furtherembodiments, when R⁴ and R⁵ are joined to form a cyclic group includingthe phosphorus atom of the N²-phosphinyl amidine group, the phosphinylgroup can be a phosphol-1-yl group; alternatively, a substitutedphosphol-1-yl group; alternatively, a 2,3-dihydrophosphol-1-yl group;alternatively, a substituted 2,3-dihydrophosphol-1-yl group;alternatively, a 3,5-dihydrophosphol-1-yl group; alternatively, asubstituted 3,5-dihydrophosphol-1-yl group; alternatively, aphospholan-1-yl group; alternatively, a substituted phospholan-1-ylgroup; alternatively, a 1,2-dihydrophosphinin-1-yl group; alternatively,a substituted, 1,2-dihydrophosphinin-1-yl group; alternatively, a1,4-dihydrophosphinin-1-yl group; alternatively, a substituted1,4-dihydrophosphinin-1-yl group; alternatively, a1,2,3,4-tetrahydro-phosphinin-1-yl group; alternatively, a substituted1,2,3,4-tetrahydrophosphinin-1-yl group; alternatively, a1,2,3,6-tetrahydrophosphinin-1-yl group; alternatively, a substituted1,2,3,6-tetrahydrophosphinin-1-yl group; alternatively, aphosphinan-1-yl group; or alternatively, a substituted phosphinan-1-ylgroup.

In an embodiment, when R⁴ and R⁵ are joined to form a cyclic groupincluding the phosphorus atom of the N²-phosphinyl amidine group, thecyclic group including the phosphorus atom can comprise at least onesubstituent on a carbon atom adjacent to the phosphorus atom attached tothe N² nitrogen atom of the N²-phosphinyl amidine group. In someembodiments, when R⁴ and R⁵ are joined to form a cyclic group includingthe phosphorus atom of the N²-phosphinylamidine group, the cyclic groupincluding the phosphorus atom can comprise at least one substituent oneach carbon atom adjacent to the phosphorus atom attached to the N²nitrogen atom of the N²-phosphinyl amidine group. In other embodiments,when R⁴ and R⁵ are joined to form a cyclic group including thephosphorus atom of the N²-phosphinyl amidine group, the cyclic groupincluding the phosphorus atom can comprise, or consist of, only onesubstituent on a carbon atom adjacent to the phosphorus atom attached tothe N² nitrogen atom of the N²-phosphinyl amidine group. In yet otherembodiments, when R⁴ and R⁵ are joined to form a cyclic group includingthe phosphorus atom of the N²-phosphinyl amidine group, the cyclic groupincluding the phosphorus atom can comprise, or consist of, only onesubstituent on each carbon atom adjacent to the phosphorus atom attachedto the N² nitrogen atom of the N²-phosphinyl amidine group.

In an embodiment, each substituent for a cyclic group including thephosphorus atom of the N²-phosphinyl amidine group independently can bea halogen, a hydrocarbyl group, a hydrocarboxy group; alternatively, ahalogen, a hydrocarbyl group; alternatively, a halogen or a hydrocarboxygroup; alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituent for a substituted cycloalkyl group which can be utilized forthe cyclic group including the phosphorus atom of the N²-phosphinylamidine group independently can be a halogen, an alkyl group, and analkoxy group; alternatively, a halogen and an alkyl group;alternatively, a halogen or an alkoxy group; alternatively, an alkylgroup or an alkoxy group; alternatively, a halogen; alternatively, analkyl group; or alternatively, an alkoxy group. Halogens, hydrocarbylgroups, hydrocarboxy groups, alkyl groups, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituents for the cyclic groupincluding the phosphorus atom of the N²-phosphinyl amidine group.

In an embodiment, R⁴ and/or R⁵ independently can be a phenyl group, a2-alkylphenyl group, a 3-alkylphenyl group, a 4-alkylphenyl group, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, a 3,5-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup, a 4-alkylphenyl group, a 2,4-dialkylphenyl group, a2,6-dialkylphenyl group, or a 2,4,6-trialkylphenyl group; alternatively,a 2-alkylphenyl group or a 4-alkylphenyl group; alternatively, a2,4-dialkylphenyl group, a 2,6-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2,4-dialkylphenyl group ora 2,6-dialkylphenyl group; alternatively, a 2,6-dialkylphenyl group, ora 2,4,6-trialkylphenyl group; alternatively, a 3-alkylphenyl group or a3,5-dialkylphenyl group; alternatively, a 2-alkylphenyl group or a2,6-dialkylphenyl group; alternatively, a 2-alkylphenyl group;alternatively, a 3-alkylphenyl group; alternatively, a 4-alkylphenylgroup; alternatively, a 2,4-dialkylphenyl group; alternatively, a2,6-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group; oralternatively, a 2,4,6-trialkylphenyl group. In another non-limitingembodiment, R⁴ and/or R⁵ independently can be a napht-1-yl group, a2-naphth-2-yl group, a 2-alkylnaphth-1-yl group, a 1-alkylnaphth-2-ylgroup, a 3-alkylnapth-2-yl group, or a 1,3-dialkylnaphth-2-yl group;alternatively, a napht-1-yl group or a 2-alkylnaphth-1-yl group;alternatively, a naphth-2-yl group, a 1-alkylnaphth-2-yl group, a3-alkylnapth-2-yl group, or a 1,3-dialkyl-naphth-2-yl group;alternatively, a napht-1-yl group; alternatively, a 2-naphth-2-yl group;alternatively, a 2-alkylnaphth-1-yl group; alternatively, a1-alkylnaphth-2-yl group; alternatively, a 3-alkylnapth-2-yl group; oralternatively, a 1,3-dialkylnaphth-2-yl group. In other non-limitingembodiments, R⁴ and/or R⁵ independently can be a cyclohexyl group, a2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group;alternatively, a cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group; alternatively, a cyclohexyl group;alternatively, a 2-alkylcyclohexyl group; alternatively, a2,6-dialkylcyclohexyl group; alternatively, cyclopentyl group;alternatively, a 2-alkylcyclopentyl group; or alternatively, a2,5-dialkylcyclopentyl group. Alkyl group substituents are independentlydescribed herein and can be utilized, without limitation, to furtherdescribe the alkylphenyl, dialkylphenyl, trialkylphenyl, naphthyl,dialkylnaphthyl, alkylcyclohexyl, dialkylcyclohexyl, alkylcyclopentyl,or dialkylcyclopentyl groups that can be utilized R⁴ and/or R⁵.Generally, the alkyl substituents of a dialkyl or trialkyl phenyl,naphthyl, cyclohexyl, or cyclopentyl group can be the same; oralternatively, the alkyl substituents of a dialkyl or trialkyl phenyl,naphthyl, cyclohexyl, or cyclopentyl group can be different.

In another non-limiting embodiment, R⁴ and/or R⁵ independently can be aphenyl group, a 2-alkoxyphenyl group, a 3-alkoxyphenyl group, a4-alkoxyphenyl group, or 3,5-dialkoxyphenyl group; alternatively, a2-alkoxyphenyl group or a 4-alkoxyphenyl group; alternatively, a3-alkoxyphenyl group or 3,5-dialkoxyphenyl group; alternatively, a2-alkoxyphenyl group; alternatively, a 3-alkoxyphenyl group;alternatively, a 4-alkoxyphenyl group; alternatively, a3,5-dialkoxyphenyl group. Alkoxy group substituents are independentlydescribed herein and may be utilized, without limitation, to furtherdescribe the alkoxyphenyl or dialkoxyphenyl groups that can be utilizedR⁴ and/or R⁵. Generally, the alkoxy substituents of a dialkoxyphenylgroups can be the same; or alternatively, the alkoxy substituents of adialkoxyphenyl group can be different.

In other non-limiting embodiments, R⁴ and/or R⁵ independently can be aphenyl group, a 2-halophenyl group, a 3-halophenyl group, a 4-halophenylgroup, a 2,6-dihalophenyl group, or a 3,5-dialkylphenyl group;alternatively, a 2-halophenyl group, a 4-halophenyl group, or a2,6-dihalophenyl group; alternatively, a 2-halophenyl group or a4-halophenyl group; alternatively, a 3-halophenyl group or a3,5-dihalophenyl group; alternatively, a 2-halophenyl group;alternatively, a 3-halophenyl group; alternatively, a 4-halophenylgroup; alternatively, a 2,6-dihalophenyl group; or alternatively, a3,5-dihalophenyl group. Halides are independently described herein andmay be utilized, without limitation, to further describe the halophenylor dihalophenyl groups that can be utilized R⁴ and/or R⁵. Generally, thehalides of a dihalophenyl group can be the same; or alternatively, thehalides of a dihalophenyl group can be different.

In a non-limiting embodiment, R⁴ and/or R⁵ independently can be a2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropylphenyl group,a 2-tert-butylphenyl group, a 3-methylphenyl group, a 2,6-dimethylphenylgroup, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 3,5-dimethyl group, or a2,4,6-trimethylphenyl group; alternatively, a 2-methylphenyl group, a2-ethylphenyl group, a 2-isopropylphenyl group, or a 2-tert-butylphenylgroup; alternatively, a 2,6-dimethylphenyl group, a 2,6-diethylphenylgroup, a 2,6-diisopropylphenyl group, or a 2,6-di-tert-butylphenylgroup; alternatively, 2-methylphenyl group; alternatively, a2-ethylphenyl group; alternatively, a 2-isopropylphenyl group;alternatively, a 2-tert-butylphenyl group; alternatively, a3-methylphenyl group; alternatively, a 2,6-dimethylphenyl group;alternatively, a 2,6-diethylphenyl group; alternatively, a2,6-diisopropylphenyl group; alternatively, a 2,6-di-tert-butylphenylgroup; alternatively, a 3,5-dimethyl group; or alternatively, a2,4,6-trimethylphenyl group. In another non-limiting embodiment, R⁴and/or R⁵ independently can be cyclohexyl group, a 2-methylcyclohexylgroup, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group; alternatively, a 2-methylcyclohexylgroup, a 2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, or a2-tert-butylcyclohexyl group; alternatively, a 2,6-dimethylcyclohexylgroup, a 2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group,or a 2,6-di-tert-butylcyclohexyl group; alternatively, a cyclohexylgroup; alternatively, a 2-methylcyclohexyl group; alternatively, a2-ethylcyclohexyl group; alternatively, a 2-isopropylcyclohexyl group;alternatively, a 2-tert-butyl-cyclohexyl group; alternatively, a2,6-dimethylcyclohexyl group; alternatively, a 2,6-diethylcyclohexylgroup; alternatively, a 2,6-diisopropylcyclohexyl group; oralternatively, a 2,6-di-tert-butylcyclohexyl group. In anothernon-limiting embodiment, R⁴ and/or R⁵ independently can be a2-methylnaphth-1-yl group, a 2-ethylnaphth-1-yl group, a2-n-propylnaphth-1-yl group, a 2-isopropylnaphth-1-yl group, or a2-tert-butylnaphth-1-yl group; alternatively, a 2-methylnaphth-1-ylgroup; alternatively, a 2-ethyl-naphth-1-yl group; alternatively, a2-n-propylnaphth-1-yl group; alternatively, a 2-isopropylnaphth-1-ylgroup; or alternatively, a 2-tert-butylnaphth-1-yl group.

In a non-limiting embodiment, R⁴ and/or R⁵ independently can be a2-methoxyphenyl group, a 2-ethoxyphenyl group, a 2-isopropoxyphenylgroup, a 2-tert-butoxyphenyl group, a 3-methoxyphenyl group, a3-ethoxyphenyl group, a 3-isopropoxyphenyl group, a 3-tert-butoxyphenylgroup, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a4-isopropoxyphenyl group, a 4-tert-butoxyphenyl group, a2,4-dimethoxyphenyl group, a 2,4-diethoxyphenyl group, a2,4-diisopropoxyphenyl group, a 2,4-di-tert-butoxyphenyl group, a3,5-dimethoxyphenyl group, a 3,5-diethoxyphenyl group, a3,5-diisopropoxyphenyl group, a 3,5-di-tert-butoxyphenyl group, a2,6-dimethoxyphenyl group, a 2,6-diethoxyphenyl group, a2,6-diisopropoxyphenyl group, a 2,6-di-tert-butoxyphenyl group, or a2,4,6-trimethoxyphenyl group; alternatively, a 2-methoxyphenyl group, a2-ethoxyphenyl group, a 2-isopropoxyphenyl group, or a2-tert-butoxyphenyl group; alternatively, a 3-methoxyphenyl group, a3-ethoxyphenyl group, a 3-isopropoxyphenyl group, or a3-tert-butoxyphenyl group; alternatively, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, or a4-tert-butoxyphenyl group; alternatively, a 2,4-dimethoxyphenyl group, a2,4-diethoxyphenyl group, a 2,4-diisopropoxyphenyl group, or a2,4-di-tert-butoxyphenyl group; alternatively, a 3,5-dimethoxyphenylgroup, a 3,5-diethoxyphenyl group, a 3,5-diisopropoxyphenyl group, or a3,5-di-tert-butoxyphenyl group; or alternatively, a 2,6-dimethoxyphenylgroup, a 2,6-diethoxyphenyl group, a 2,6-diisopropoxyphenyl group, or a2,6-di-tert-butoxyphenyl group. In other non-limiting embodiments, R⁴and/or R⁵ independently can be a 2-methoxyphenyl group; alternatively, a2-ethoxyphenyl group; alternatively, a 2-isopropoxyphenyl group;alternatively, a 2-tert-butoxyphenyl group; alternatively, a3-methoxyphenyl group; alternatively, a 3-ethoxyphenyl group;alternatively, a 3-isopropoxyphenyl group; alternatively, a3-tert-butoxyphenyl group; alternatively, a 4-methoxyphenyl group;alternatively, a 4-ethoxyphenyl group; alternatively, a4-isopropoxyphenyl group; alternatively, a 4-tert-butoxyphenyl group;alternatively, a 2,4-dimethoxyphenyl group; alternatively, a2,4-diethoxyphenyl group; alternatively, a 2,4-diisopropoxyphenyl group;alternatively, a 2,4-di-tert-butoxyphenyl group; alternatively, a3,5-dimethoxyphenyl group; alternatively, a 3,5-diethoxyphenyl group;alternatively, a 3,5-diisopropoxyphenyl group; alternatively, a3,5-di-tert-butoxyphenyl group; alternatively, a 2,6-dimethoxyphenylgroup; alternatively, a 2,6-diethoxyphenyl group; alternatively, a2,6-diisopropoxyphenyl group; alternatively, a 2,6-di-tert-butoxyphenylgroup; or alternatively, a 2,4,6-trimethoxyphenyl group.

In another non-limiting embodiment, R⁴ and/or R⁵ independently can be a2-fluorophenyl group, a 2-chlorophenyl group, a 3-fluorophenyl group, a3-chlorophenyl group, a 4-fluorophenyl group, a 4-chlorophenyl group, a3,5-difluorophenyl group, or a 3,5-dichlorophenyl group; alternatively,a 2-fluorophenyl group or a 2-chlorophenyl group; alternatively, a3-fluorophenyl group or a 3-chlorophenyl group; alternatively, a4-fluorophenyl group or a 4-chlorophenyl group; alternatively, a3,5-difluorophenyl group or a 3,5-dichlorophenyl group; alternatively, a3-fluorophenyl group, a 3-chlorophenyl group, a 3,5-difluorophenyl groupor a 3,5-dichlorophenyl group; or alternatively, a 3-fluorophenyl groupor a 3,5-difluorophenyl group. In another non-limiting embodiments, R⁴and/or R⁵ independently can be a 2-fluorophenyl group; alternatively, a2-chlorophenyl group; alternatively, a 3-fluorophenyl group;alternatively, a 3-chlorophenyl group; alternatively, a 4-fluorophenylgroup; alternatively, a 4-chlorophenyl; alternatively, a3,5-difluorophenyl group; or alternatively, a 3,5-dichlorophenyl group.

Generally, the R⁴ and/or R⁵ groups of the phosphinyl group independentlycan be any R⁴ or R⁵ group described herein and utilized in anycombination to further describe the phosphinyl group of anyN²-phosphinyl amidine compound described herein. In an embodiment, R⁴and R⁵ can be the same. In other embodiments R⁴ and R⁵ can be different.

In an aspect, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a diphenylphosphinyl group, a dialkylphosphinyl group, abis(mono-halo substituted phenyl)phosphinyl group, a bis(mono-alkylsubstituted phenyl)phosphinyl group, or a bis(mono-alkoxy substitutedphenyl)-phosphinyl group; alternatively, a diphenylphosphinyl group;alternatively, a dialkylphosphinyl group; alternatively, a bis(mono-halosubstituted phenyl)phosphinyl group; alternatively, a bis(mono-alkylsubstituted phenyl)phosphinyl group; alternatively, a bis(mono-alkoxysubstituted phenyl)phosphinyl group. In another aspect, the phosphinylgroup of the N²-phosphinyl amidine compound can be an(alkyl)(phenyl)phosphinyl group, a (mono-halo substitutedphenyl)(phenyl)phosphinyl group, a (mono-alkyl substitutedphenyl)(phenyl)phosphinyl group, a (mono-alkoxy substitutedphenyl)(phenyl)-phosphinyl group, a (mono-alkyl substitutedphenyl)(mono-halo substituted phenyl) phosphinyl group, or a (mono-alkylsubstituted phenyl)(mono-alkoxy substituted phenyl) phosphinyl group;alternatively, an (alkyl)(phenyl)phosphinyl group; alternatively, a(mono-halo substituted phenyl)(phenyl)phosphinyl group; alternatively, a(mono-alkyl substituted phenyl)(phenyl)phosphinyl group; alternatively,a (mono-alkoxy substituted phenyl)(phenyl)phosphinyl group;alternatively, a (mono-alkyl substituted phenyl)-(mono-halo substitutedphenyl) phosphinyl group; or alternatively, a (mono-alkyl substitutedphenyl)-(mono-alkoxy substituted phenyl) phosphinyl group. In anotheraspect, the phosphinyl group of the N²-phosphinyl amidine compound canbe a bis(dihalo substituted phenyl)phosphinyl group, a bis(dialkylsubstituted phenyl)phosphinyl group, a bis(dialkoxy substitutedphenyl)phosphinyl group, a bis(trialkyl-phenyl)phosphinyl group, or abis(trialkoxyphenyl)phosphinyl group; alternatively, bis(dihalosubstituted phenyl)phosphinyl group; alternatively, a bis(dialkylsubstituted phenyl)phosphinyl group; alternatively, a bis(dialkoxysubstituted phenyl)phosphinyl group; alternatively, abis(trialkylphenyl)phosphinyl group; or alternatively, abis(trialkoxyphenyl)phosphinyl group. Halogens, alkyl groups, and alkoxygroups are independently described herein (e.g. as substituents forsubstituted R¹ groups) and can be utilized, without limitation tofurther describe the phosphinyl group which can be utilized in theN²-phosphinyl amidine compound.

In a non-limiting aspect, the phosphinyl group of the N²-phosphinylamidine compound can be a dimethylphosphinyl group, a diethylphosphinylgroup, a diisopropylphosphinyl group, a di-tert-butylphosphinyl group,or a di-neo-pentylphosphinyl group. In a non-limiting embodiment, thephosphinyl group of the N²-phosphinyl amidine compound can be adimethylphosphinyl group; alternatively, a diethyl phosphinyl group;alternatively, a diisopropylphosphinyl group; alternatively, adi-tert-butyl-phosphinyl group; or alternatively, adi-neo-pentylphosphinyl group.

In a non-limiting aspect, the phosphinyl group of the N²-phosphinylamidine compound can be a (methyl)(phenyl)phosphinyl group, a(ethyl)(phenyl)phosphinyl group, a (isopropyl)(phenyl)phosphinyl group,a (tert-butyl)(phenyl)phosphinyl group, or a(neo-pentyl)(phenyl)phosphinyl group. In an embodiment, the phosphinylgroup of the N²-phosphinyl amidine compound can be a(methyl)(phenyl)-phosphinyl group; alternatively, a (ethyl)(phenyl)phosphinyl group; alternatively, a (isopropyl)(phenyl)phosphinyl group;alternatively, a (tert-butyl)(phenyl)phosphinyl group; or alternatively,a (neo-pentyl)(phenyl)phosphinyl group.

In some non-limiting embodiments, the phosphinyl group of theN²-phosphinyl amidine compound can be a dicyclopentyl phosphinyl group,a dicyclohexyl phosphinyl group; alternatively, adicyclopentylphosphinyl group; or alternatively, adicyclohexylphosphinyl group.

In yet another non non-limiting aspect, the phosphinyl group of theN²-phosphinyl amidine compound can be a bis(2-fluorophenyl)phosphinylgroup, a bis(2-chlorophenyl)phosphinyl group, abis(3-fluorophenyl)phosphinyl group, a bis(3-chlorophenyl)phosphinylgroup, a bis(4-fluorophenyl)-phosphinyl group, or abis(4-chlorophenyl)phosphinyl group. In some non-limiting embodiments,the phosphinyl group of the N²-phosphinyl amidine compound can be abis(2-fluorophenyl)phosphinyl group, a bis(3-fluorophenyl)phosphinylgroup, or a bis(4-fluorophenyl)phosphinyl group; or alternatively, abis(2-chlorophenyl)phosphinyl group, a bis(3-chlorophenyl)phosphinylgroup, or a bis(4-chlorophenyl)-phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a bis(2-fluorophenyl)phosphinyl group; alternatively, abis(2-chlorophenyl)-phosphinyl group; alternatively, abis(3-fluorophenyl)phosphinyl group; alternatively, abis(3-chloro-phenyl)phosphinyl group; alternatively, abis(4-fluorophenyl)phosphinyl group; or alternatively, abis(4-chlorophenyl)phosphinyl group.

In yet another non non-limiting aspect, the phosphinyl group of theN²-phosphinyl amidine compound can be a(2-fluorophenyl)(phenyl)phosphinyl group, a(2-chlorophenyl)(phenyl)phosphinyl group, a(3-fluorophenyl)(phenyl)phosphinyl group, a(3-chlorophenyl)(phenyl)phosphinyl group, a(4-fluorophenyl)(phenyl)phosphinyl group, or a(4-chlorophenyl)(phenyl)phosphinyl group. In some non-limitingembodiments, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a (2-fluorophenyl)(phenyl)phosphinyl group, a(3-fluorophenyl)(phenyl)phosphinyl group, or a(4-fluoro-phenyl)(phenyl)phosphinyl group; or alternatively, a(2-chlorophenyl)(phenyl)phosphinyl group, a(3-chlorophenyl)(phenyl)phosphinyl group, or a(4-chlorophenyl)(phenyl)phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a (2-fluorophenyl)(phenyl)phosphinyl group; alternatively, a(2-chlorophenyl)(phenyl)phosphinyl group; alternatively, a(3-fluorophenyl)(phenyl)phosphinyl group; alternatively, a(3-chlorophenyl)(phenyl)-phosphinyl group; alternatively, a(4-fluorophenyl)(phenyl)phosphinyl group; or alternatively, a(4-chlorophenyl)(phenyl)phosphinyl group.

In yet another non non-limiting aspect, the phosphinyl group of theN²-phosphinyl amidine compound can be a diphenylphosphinyl group, abis(2-methylphenyl)phosphinyl group, a bis(2-ethyl-phenyl)phosphinylgroup, a bis(2-isopropylphenyl)phosphinyl group, abis(2-tert-butylphenyl)phosphinyl group, a bis(3-methylphenyl)phosphinylgroup, a bis(3-ethylphenyl)phosphinyl group,bis(3-isopropyl-phenyl)phosphinyl group, abis(3-tert-butylphenyl)phosphinyl group, a diphenylphosphinyl group, abis(4-methylphenyl)phosphinyl group, a bis(4-ethylphenyl)phosphinylgroup, a bis(4-isopropylphenyl)-phosphinyl group, or abis(4-tert-butylphenyl)phosphinyl group. In a non-limiting embodiment,the phosphinyl group of the N²-phosphinyl amidine compound can be abis(2-methylphenyl)phosphinyl group, a bis(2-ethylphenyl)phosphinylgroup, a bis(2-isopropylphenyl)phosphinyl group, or abis(2-tert-butylphenyl)phosphinyl group; alternatively, adiphenylphosphinyl group, a bis(3-methyl-phenyl)phosphinyl group, abis(3-ethylphenyl)phosphinyl group, a bis(3-isopropylphenyl)phosphinylgroup, or a bis(3-tert-butylphenyl)phosphinyl group; or alternatively, adiphenylphosphinyl group, a bis(4-methylphenyl)phosphinyl group, abis(4-ethylphenyl)phosphinyl group, a bis(4-isopropyl-phenyl)phosphinylgroup, or a bis(4-tert-butylphenyl)phosphinyl group. In othernon-limiting embodiments, the phosphinyl group of the N²-phosphinylamidine compound can be a diphenyl-phosphinyl group; alternatively, abis(2-methylphenyl)phosphinyl group; alternatively, abis(2-ethyl-phenyl)phosphinyl group; alternatively, abis(2-isopropylphenyl)phosphinyl group; alternatively, abis(2-tert-butylphenyl)phosphinyl group; alternatively, abis(3-methylphenyl)phosphinyl group; alternatively, abis(3-ethylphenyl)phosphinyl group; alternatively, abis(3-isopropylphenyl)phosphinyl group; alternatively, abis(3-tert-butylphenyl)phosphinyl group; alternatively, adiphenylphosphinyl group; alternatively, a bis(4-methylphenyl)phosphinylgroup; alternatively, a bis(4-ethylphenyl)-phosphinyl group;alternatively, a bis(4-isopropylphenyl)phosphinyl group; oralternatively, a bis(4-tert-butylphenyl)phosphinyl group.

In yet another non non-limiting aspect, the phosphinyl group of theN²-phosphinyl amidine compound can be a diphenylphosphinyl group, a(2-methylphenyl)(phenyl)phosphinyl group, a(2-ethyl-phenyl)(phenyl)phosphinyl group, a(2-isopropylphenyl)(phenyl)phosphinyl group, a(2-tert-butyl-phenyl)(phenyl)phosphinyl group, a(3-methylphenyl)(phenyl)phosphinyl group, a(3-ethylphenyl)-(phenyl)phosphinyl group,(3-isopropylphenyl)(phenyl)phosphinyl group, a(3-tert-butylphenyl)(phenyl)-phosphinyl group, a diphenylphosphinylgroup, a (4-methylphenyl)(phenyl)phosphinyl group, a(4-ethyl-phenyl)(phenyl)phosphinyl group, a(4-isopropylphenyl)(phenyl)phosphinyl group, or a(4-tert-butyl-phenyl)(phenyl)phosphinyl group. In a non-limitingembodiment, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a (2-methylphenyl)(phenyl)phosphinyl group, a(2-ethyl-phenyl)(phenyl)phosphinyl group,(2-isopropylphenyl)(phenyl)phosphinyl group, or a(2-tert-butyl-phenyl)(phenyl)phosphinyl group; alternatively, adiphenylphosphinyl group, a (3-methylphenyl)-(phenyl)phosphinyl group, a(3-ethylphenyl)(phenyl)phosphinyl group, a(3-isopropylphenyl)(phenyl)-phosphinyl group, or a(3-tert-butylphenyl)(phenyl)phosphinyl group; or alternatively, adiphenyl-phosphinyl group, a (4-methylphenyl)(phenyl)phosphinyl group, a(4-ethylphenyl)(phenyl)phosphinyl group, a(4-isopropylphenyl)(phenyl)phosphinyl group, or a(4-tert-butylphenyl)(phenyl)phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a diphenylphosphinyl group; alternatively, a(2-methylphenyl)(phenyl)phosphinyl group; alternatively, a(2-ethylphenyl)(phenyl)phosphinyl group; alternatively, a(2-isopropylphenyl)-(phenyl)phosphinyl group; alternatively, a(2-tert-butylphenyl)(phenyl)phosphinyl group; alternatively, a(3-methylphenyl)(phenyl)phosphinyl group; alternatively, a(3-ethylphenyl)(phenyl)phosphinyl group; alternatively, a(3-isopropylphenyl)(phenyl)phosphinyl group; alternatively, a(3-tert-butylphenyl)-(phenyl)phosphinyl group; alternatively, adiphenylphosphinyl group; alternatively, a(4-methylphenyl)-(phenyl)phosphinyl group; alternatively, a(4-ethylphenyl)(phenyl)phosphinyl group,(4-isopropyl-phenyl)(phenyl)phosphinyl group; or alternatively, a(4-tert-butylphenyl)(phenyl)phosphinyl group.

In yet another non non-limiting aspect, the phosphinyl group of theN²-phosphinyl amidine compound can be a diphenylphosphinyl group, abis(2-methoxyphenyl)phosphinyl group, a bis(2-ethoxy-phenyl)phosphinylgroup, a bis(2-isopropoxyphenyl)phosphinyl group, abis(2-tert-butoxyphenyl)-phosphinyl group, abis(3-methoxyphenyl)phosphinyl group, a bis(3-ethoxyphenyl)phosphinylgroup, a bis(3-isopropoxyphenyl)phosphinyl group, abis(3-tert-butoxyphenyl)phosphinyl group, a diphenoxy-phosphinyl group,a bis(4-methoxyphenyl)phosphinyl group, a bis(4-ethoxyphenyl)phosphinylgroup, bis(4-isopropoxyphenyl)phosphinyl group, or abis(4-tert-butoxyphenyl)phosphinyl group. In a non-limiting embodiment,the phosphinyl group of the N²-phosphinyl amidine compound can be abis(2-methoxyphenyl)phosphinyl group, a bis(2-ethoxyphenyl)phosphinylgroup, a bis(2-isopropoxy-phenyl)phosphinyl group, or abis(2-tert-butoxyphenyl)phosphinyl group; alternatively, adiphenoxy-phosphinyl group, a bis(3-methoxyphenyl)phosphinyl group, abis(3-ethoxyphenyl)phosphinyl group, a bis(3-isopropoxyphenyl)phosphinylgroup, or a bis(3-tert-butoxyphenyl)phosphinyl group; or alternatively,a diphenoxyphosphinyl group, a bis(4-methoxyphenyl)phosphinyl group, abis(4-ethoxy-phenyl)phosphinyl group, abis(4-isopropoxyphenyl)phosphinyl group, or abis(4-tert-butoxyphenyl)-phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a diphenylphosphinyl group; alternatively, abis(2-methoxyphenyl)phosphinyl group; alternatively, abis(2-ethoxyphenyl)phosphinyl group; alternatively, abis(2-isopropoxyphenyl)-phosphinyl group; alternatively, abis(2-tert-butoxyphenyl)phosphinyl group; alternatively, abis(3-methoxyphenyl)phosphinyl group; alternatively, abis(3-ethoxyphenyl)phosphinyl group; alternatively, abis(3-isopropoxyphenyl)phosphinyl group; alternatively, abis(3-tert-butoxyphenyl)-phosphinyl group; alternatively, adiphenoxyphosphinyl group; alternatively, abis(4-methoxyphenyl)-phosphinyl group; alternatively, abis(4-ethoxyphenyl)phosphinyl group; alternatively, abis(4-isopropoxyphenyl)phosphinyl group; or alternatively, abis(4-tert-butoxyphenyl)phosphinyl group.

In yet another non non-limiting aspect, the phosphinyl group of theN²-phosphinyl amidine compound can be a diphenylphosphinyl group, a(2-methoxyphenyl)(phenyl)phosphinyl group, a(2-ethoxyphenyl)(phenyl)phosphinyl group, a(2-isopropoxyphenyl)(phenyl)phosphinyl group, a(2-tert-butoxyphenyl)(phenyl)phosphinyl group, a(3-methoxyphenyl)(phenyl)phosphinyl group, a(3-ethoxyphenyl)(phenyl)phosphinyl group, a(3-isopropoxyphenyl)(phenyl)phosphinyl group, a(3-tert-butoxyphenyl)(phenyl)phosphinyl group, a diphenoxyphosphinylgroup, a (4-methoxyphenyl)-(phenyl)phosphinyl group, a(4-ethoxyphenyl)(phenyl)phosphinyl group, a(4-isopropoxyphenyl)-(phenyl)phosphinyl group, or a(4-tert-butoxyphenyl)(phenyl)phosphinyl group. In a non-limitingembodiment, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a (2-methoxy-phenyl)(phenyl)phosphinyl group, a(2-ethoxyphenyl)(phenyl)phosphinyl group,(2-isopropoxyphenyl)-(phenyl)phosphinyl group, or a(2-tert-butoxyphenyl)(phenyl)phosphinyl group; alternatively, adiphenoxyphosphinyl group, a (3-methoxyphenyl)(phenyl)phosphinyl group,a (3-ethoxyphenyl)-(phenyl)phosphinyl group, a(3-isopropoxyphenyl)(phenyl)phosphinyl group, or a(3-tert-butoxyphenyl)-(phenyl)phosphinyl group; or alternatively, adiphenoxyphosphinyl group, a (4-methoxyphenyl)(phenyl)-phosphinyl group,a (4-ethoxyphenyl)(phenyl)phosphinyl group,(4-isopropoxyphenyl)(phenyl)-phosphinyl group, or a(4-tert-butoxyphenyl)(phenyl)phosphinyl group. In other non-limitingembodiments, the phosphinyl group of the N²-phosphinyl amidine compoundcan be a diphenyl-phosphinyl group; alternatively, a(2-methoxyphenyl)(phenyl)phosphinyl group; alternatively, a(2-ethoxyphenyl)(phenyl)phosphinyl group; alternatively, a(2-isopropoxyphenyl)(phenyl)phosphinyl group; alternatively, a(2-tert-butoxyphenyl)(phenyl)phosphinyl group; alternatively, a(3-methoxy-phenyl)(phenyl)phosphinyl group; alternatively, a(3-ethoxyphenyl)(phenyl)phosphinyl group; alternatively, a(3-isopropoxyphenyl)(phenyl)phosphinyl group; alternatively, a(3-tert-butoxyphenyl)-(phenyl)phosphinyl group; alternatively, adiphenoxyphosphinyl group; alternatively, a(4-methoxy-phenyl)(phenyl)phosphinyl group; alternatively, a(4-ethoxyphenyl)(phenyl)phosphinyl group,(4-isopropoxyphenyl)(phenyl)phosphinyl group; or alternatively, a(4-tert-butoxyphenyl)(phenyl)-phosphinyl group.

Generally, D¹ can be a q valent organic group; alternatively, a q valentan organic group consisting essentially of inert functional groups; oralternatively, a q valent hydrocarbon group. In an aspect, D¹ can be a qvalent C₁ to C₃₀ organic group; alternatively, a q valent C₁ to C₂₀organic group; alternatively, a q valent C₁ to C₁₅ organic group;alternatively, a q valent C₁ to C₁₀ organic group; or alternatively, a qvalent C₁ to C₅ organic group. In another aspect, D¹ can be a q valentC₁ to C₃₀ organic group consisting essentially of inert functionalgroups; alternatively, a q valent C₁ to C₂₀ organic group consistingessentially of inert functional groups; alternatively, a q valent C₁ toC₁₅ organic group consisting essentially of inert functional groups;alternatively, a q valent C₁ to C₁₀ organic group consisting essentiallyof inert functional groups; or alternatively, a q valent C₁ to C₅organic group consisting essentially of inert functional groups. In yetanother aspect, D¹ can be a q valent C₁ to C₃₀ hydrocarbyl group;alternatively, a q valent C₁ to C₂₀ hydrocarbyl group; alternatively, aq valent C₁ to C₁₅ hydrocarbyl group; alternatively, a q valent C₁ toC₁₀ hydrocarbyl group; or alternatively, a q valent C₁ to C₅ hydrocarbylgroup. In yet other aspects, D¹ can be a q valent C₃ to C₃₀ aromaticgroup; alternatively, a q valent C₃ to C₂₀ aromatic group;alternatively, a q valent C₃ to C₁₅ aromatic group; or alternatively, aq valent C₃ to C₁₀ aromatic group.

In an aspect, q can be an integer greater than zero. In someembodiments, q can be an integer from 1 to 5; alternatively, an integerfrom 1 to 4; or alternatively, 2 or 3. In other embodiments, q can be 1;alternatively, 2; alternatively, 3; alternatively, 4; or alternatively,5.

In an aspect, L¹ can be a C₁ to C₃₀ organylene group; alternatively, aC₁ to C₂₀ organylene group; alternatively, a C₁ to C₁₅ organylene group;alternatively, a C₁ to C₁₀ organylene group; or alternatively, a C₁ toC₅ organylene group. In another aspect, L¹ can be a C₁ to C₃₀ organylenegroup consisting essentially of inert functional groups; alternatively,a C₁ to C₂₀ organylene group consisting essentially of inert functionalgroups; alternatively, a C₁ to C₁₅ organylene group consistingessentially of inert functional groups; alternatively, a C₁ to C₁₀organylene group; or alternatively, a C₁ to C₅ organylene groupconsisting essentially of inert functional groups. In yet anotheraspect, L¹ can be a C₁ to C₃₀ hydrocarbylene group; alternatively, a C₁to C₂₀ hydrocarbylene group; alternatively, a C₁ to C₁₅ hydrocarbylenegroup; alternatively, a C₁ to C₁₀ hydrocarbylene group; oralternatively, a C₁ to C₅ hydrocarbylene group. In yet other aspects, L¹can be a C₃ to C₃₀ aromatic group; alternatively, a C₃ to C₂₀ aromaticgroup; alternatively, a C₃ to C₁₅ aromatic group; or alternatively, a C₃to C₁₀ aromatic group.

In an aspect, L¹ can be a C₁ to C₃₀ alkylene group, a C₄ to C₃₀cycloalkylene group, a C₄ to C₃₀ substituted cycloalkylene group, a C₃to C₃₀ aliphatic heterocyclylene group, a C₃ to C₃₀ substitutedaliphatic heterocyclylene group, a C₆ to C₃₀ arylene group, a C₆ to C₃₀substituted arylene group, a C₃ to C₃₀ heteroarylene group, or a C₃ toC₃₀ substituted heteroarylene group; alternatively, a C₁ to C₃₀ alkylenegroup, a C₄ to C₃₀ cycloalkylene group, a C₄ to C₃₀ substitutedcycloalkylene group, a C₆ to C₃₀ arylene group, or a C₆ to C₃₀substituted arylene group; alternatively, a C₄ to C₃₀ cycloalkylenegroup or a C₄ to C₃₀ substituted cycloalkylene group; alternatively, aC₃ to C₃₀ aliphatic heterocyclylene group or a C₃ to C₃₀ substitutedaliphatic heterocyclylene group; alternatively, a C₆ to C₃₀ arylenegroup or a C₆ to C₃₀ substituted arylene group; alternatively, a C₃ toC₃₀ heteroarylene group or a C₃ to C₃₀ substituted heteroarylene group;alternatively, a C₁ to C₃₀ alkylene group; alternatively, a C₄ to C₃₀cycloalkylene group; alternatively, a C₄ to C₃₀ substitutedcycloalkylene group; alternatively, a C₃ to C₃₀ aliphaticheterocyclylene group; alternatively, a C₃ to C₃₀ substituted aliphaticheterocyclylene group; alternatively, a C₆ to C₃₀ arylene group;alternatively, a C₆ to C₃₀ substituted arylene group; alternatively, aC₃ to C₃₀ heteroarylene group; or alternatively, a C₃ to C₃₀ substitutedheteroarylene group. In an embodiment, L¹ can be a C₁ to C₁₅ alkylenegroup, a C₄ to C₂₀ cycloalkylene group, a C₄ to C₂₀ substitutedcycloalkylene group, a C₃ to C₂₀ aliphatic heterocyclylene group, a C₃to C₂₀ substituted aliphatic heterocyclylene group, a C₆ to C₂₀ arylenegroup, a C₆ to C₂₀ substituted arylene group, a C₃ to C₂₀ heteroarylenegroup, or a C₃ to C₂₀ substituted heteroarylene group; alternatively, aC₁ to C₁₅ alkylene group, a C₄ to C₂₀ cycloalkylene group, a C₄ to C₂₀substituted cycloalkylene group, a C₆ to C₂₀ arylene group, or a C₆ toC₂₀ substituted arylene group; alternatively, a C₄ to C₂₀ cycloalkylenegroup or a C₄ to C₂₀ substituted cycloalkylene group; alternatively, aC₃ to C₂₀ aliphatic heterocyclylene group or a C₃ to C₂₀ substitutedaliphatic heterocyclylene group; alternatively, a C₆ to C₂₀ arylenegroup or a C₆ to C₂₀ substituted arylene group; alternatively, a C₃ toC₂₀ heteroarylene group or a C₃ to C₂₀ substituted heteroarylene group;alternatively, a C₁ to C₁₅ alkylene group; alternatively, a C₄ to C₂₀cycloalkylene group; alternatively, a C₄ to C₂₀ substitutedcycloalkylene group; alternatively, a C₃ to C₂₀ aliphaticheterocyclylene group; alternatively, a C₃ to C₂₀ substituted aliphaticheterocyclylene group; alternatively, a C₆ to C₂₀ arylene group;alternatively, a C₆ to C₂₀ substituted arylene group; alternatively, aC₃ to C₂₀ heteroarylene group; or alternatively, a C₃ to C₂₀ substitutedheteroarylene group. In other embodiments, L¹ be a C₁ to C₁₀ alkylenegroup, a C₄ to C₁₅ cycloalkylene group, a C₄ to C₁₅ substitutedcycloalkylene group, a C₃ to C₁₅ aliphatic heterocyclylene group, a C₃to C₁₅ substituted aliphatic heterocyclylene group, a C₆ to C₁₅ arylenegroup, a C₆ to C₁₅ substituted arylene group, a C₃ to C₁₅ heteroarylenegroup, or a C₃ to C₁₅ substituted heteroarylene group; alternatively, aC₁ to C₁₀ alkylene group, a C₄ to C₁₅ cycloalkylene group, a C₄ to C₁₅substituted cycloalkylene group, a C₆ to C₁₅ arylene group, or a C₆ toC₁₅ substituted arylene group; alternatively, a C₄ to C₁₅ cycloalkylenegroup or a C₄ to C₁₅ substituted cycloalkylene group; alternatively, aC₃ to C₁₅ aliphatic heterocyclylene group or a C₃ to C₁₅ substitutedaliphatic heterocyclylene group; alternatively, a C₆ to C₁₅ arylenegroup or a C₆ to C₁₅ substituted arylene group; alternatively, a C₃ toC₁₅ heteroarylene group or a C₃ to C₁₅ substituted heteroarylene group;alternatively, a C₁ to C₁₀ alkylene group; alternatively, a C₄ to C₁₅cycloalkylene group; alternatively, a C₄ to C₁₅ substitutedcycloalkylene group; alternatively, a C₃ to C₁₅ aliphaticheterocyclylene group; alternatively, a C₃ to C₁₅ substituted aliphaticheterocyclylene group; alternatively, a C₆ to C₁₅ arylene group;alternatively, a C₆ to C₁₅ substituted arylene group; alternatively, aC₃ to C₁₅ heteroarylene group; or alternatively, a C₃ to C₁₅ substitutedheteroarylene group. In further embodiments, L¹ can be a C₁ to C₅alkylene group.

In an embodiment, L¹ can be a methylene group, an ethylene group, apropylene group, a butylene group, a pentylene group, a hexylene group,a heptylene group, an octylene group, a nonylene group, a decylenegroup, a undecylene group, a dodecylene group, a tridecylene group, atetradecylene group, a pentadecylene group, a hexadecylene group, aheptadecylene group, an octadecylene group, or a nonadecylene group; oralternatively, a methylene group, an ethylene group, a propylene group,a butylene group, a pentylene group, a hexylene group, a heptylenegroup, an octylene group, a nonylene group, a decylene group. In someembodiments, L¹ can be a methylene group, an ethylene group, a propylenegroup, a butylene group, or a pentylene group. In other embodiments, L¹can be a methylene group; alternatively, an ethylene group;alternatively, a propylene group; alternatively, a butylene group;alternatively, a pentylene group; alternatively, a hexylene group;alternatively, a heptylene group; alternatively, an octylene group;alternatively, a nonylene group; alternatively, a decylene group;alternatively, a undecylene group; alternatively, a dodecylene group;alternatively, a tridecylene group; alternatively, a tetradecylenegroup; alternatively, a pentadecylene group; alternatively, ahexadecylene group; alternatively, a heptadecylene group; alternatively,an octadecylene group; or alternatively, a nonadecylene group. In someembodiments, L¹ can be a eth-1,2-ylene group, a prop-1,3-ylene group, abut-1,4-ylene group, a but-2,3-ylene group, a pent-1,5-ylene group, a2,2-dimethylprop-1,3-ylene group, a hex-1,6-ylene group, or a2,3-dimethylbut-2,3-ylene group; alternatively, a eth-1,2-ylene group, aprop-1,3-ylene group, a but-1,4-ylene group, a pent-1,5-ylene group, ora hex-1,6-ylene group; alternatively, a eth-1,2-ylene group;alternatively, a prop-1,3-ylene group; alternatively, a but-1,4-ylenegroup; alternatively, a but-2,3-ylene group; alternatively, apent-1,5-ylene group; alternatively, a 2,2-dimethylprop-1,3-ylene group;alternatively, a hex-1,6-ylene group; or alternatively, a2,3-dimethyl-but-2,3-ylene group. In some embodiments, the alkylenegroups which can be utilized as L¹ can be substituted. Each substituentof a substituted alkylene group independently can be a halogen or ahydrocarboxy group; alternatively, a halogen; or alternatively, ahydrocarboxy group. Halogens and hydrocarboxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe the substituted alkylene group which canbe utilized as L¹.

In an aspect, L¹ can have the formula—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)— wherein each R^(1a), R^(2a),R^(3a), and R^(4a) independently can be a hydrogen, a halogen, a C₁ toC₅ alkyl group, or a C₁ to C₅ alkoxy group and t can be zero or aninteger ranging from 1 to 28. In an embodiment, R^(1a), R^(2a), R^(3a),and R^(4a) independently can be hydrogen, a halogen, and a C₁ to C₅alkyl group; alternatively, hydrogen, a halogen, or a C₁ to C₅ alkoxygroup; alternatively, hydrogen, a C₁ to C₅ alkyl group, or a C₁ to C₅alkoxy group; alternatively, hydrogen or a halogen; alternatively,hydrogen or a C₁ to C₅ alkyl group; alternatively, hydrogen or a C₁ toC₅ alkoxy group; alternatively, hydrogen; or alternatively, a C₁ to C₅alkyl group. In an embodiment, t can be an integer ranging from 1 to 18;alternatively, 1 to 13; alternatively, 1 to 8; or alternatively, 1 to 3.In other embodiments, t can be zero. Halogens, C₁ to C₅ alkyl groups,and C₁ to C_(s) alkoxy groups that can be utilized as substitutents areindependently described herein and can be utilized, without limitation,to further describe L¹ having the formula—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—. In another aspect, L¹ may havethe formula —(CH₂)_(s)— wherein s can be an integer ranging from 1 to30. In an embodiment, s can be an integer ranging from 1 to 20;alternatively, 1 to 15; alternatively, 1 to 10; or alternatively, 1 to5.

In an aspect, L¹ can be any L¹ group described herein (or D¹ can be anyD¹ group described herein) wherein one or more carbon atoms of L¹attached to the N¹ nitrogen atom of the N²-phosphinyl amidine group (oneor more carbon atoms of D¹ attached to the N¹ nitrogen atom of theN²-phosphinyl amidine group) can be a tertiary carbon atom or aquaternary carbon atom; alternatively, a tertiary carbon atom; oralternatively, a quaternary carbon atom. In an embodiment, each carbonatom of L¹ attached to the N¹ nitrogen atom of the N²-phosphinyl amidinegroup (or each carbon atom of D¹ attached to the N¹ nitrogen atom of theN²-phosphinyl amidine group) can be a tertiary carbon atom or aquaternary carbon atom; alternatively, a tertiary carbon atom; oralternatively, a quaternary carbon atom.

In an embodiment, L¹ can be a cyclobutylene group, a substitutedcyclobutylene group, a cyclopentylene group, a substitutedcyclopentylene group, a cyclohexylene group, a substituted cyclohexylenegroup, a cycloheptylene group, a substituted cycloheptylene group, acyclooctylene group, or a substituted cyclooctylene group. In someembodiments, L¹ can be a cyclopentylene group, a substitutedcyclopentylene group, a cyclohexylene group, a substituted cyclohexylenegroup. In other embodiments, L¹ can be a cyclobutylene group or asubstituted cyclobutylene group; alternatively, a cyclopentylene groupor a substituted cyclopentylene group; alternatively, a cyclohexylenegroup or a substituted cyclohexylene group; alternatively, acycloheptylene group or a substituted cycloheptylene group; oralternatively, a cyclooctylene group, or a substituted cyclooctylenegroup. In further embodiments, L¹ can be a cyclopentylene group;alternatively, a substituted cyclopentylene group; a cyclohexylenegroup; or alternatively, a substituted cyclohexylene group.

In an embodiment, L¹ can be a cyclopent-1,3-ylene group, a substitutedcyclopent-1,3-ylene group, a cyclohex-1,3-ylene group, a substitutedcyclohex-1,3-ylene group, a cyclohex-1,4-ylene group, or a substitutedcyclohex-1,4-ylene group; alternatively, a cyclopent-1,3-ylene group, acyclohex-1,3-ylene group, or a cyclohex-1,4-ylene group. In someembodiments, L¹ can be a cyclopent-1,3-ylene group or a substitutedcyclopent-1,3-ylene group; alternatively, a cyclohex-1,3-ylene group, asubstituted cyclohex-1,3-ylene group, a cyclohex-1,4-ylene group, or asubstituted cyclohex-1,4-ylene group; alternatively, acyclohex-1,3-ylene group or a substituted cyclohex-1,3-ylene group;alternatively, a cyclohex-1,4-ylene group or a substitutedcyclohex-1,4-ylene group; alternatively, a cyclopent-1,3-ylene group, acyclohex-1,3-ylene group, or a cyclohex-1,4-ylene group; oralternatively, a substituted cyclopent-1,3-ylene group, a substitutedcyclohex-1,3-ylene group, or a substituted cyclohex-1,4-ylene group. Inother embodiments, L¹ can be a cyclopent-1,3-ylene group; alternatively,a substituted cyclopent-1,3-ylene group; alternatively, acyclohex-1,3-ylene group; alternatively, a substitutedcyclohex-1,3-ylene group; alternatively, a cyclohex-1,4-ylene group; oralternatively, a substituted cyclohex-1,4-ylene group.

In a non-limiting embodiment, L¹ can be a 2-substitutedcyclopen-1,3-ylene group, a 4,5-disubstituted cyclopen-1,3-ylene group,a 2,5-disubstituted cyclopen-1,3-ylene group, or a 2,4,5-trisubstitutedcyclopen-1,3-ylene group. In some embodiments, L¹ can be a 2-substitutedcyclopen-1,3-ylene group; alternatively, a 4,5-disubstitutedcyclopen-1,3-ylene group; alternatively, a 2,5-disubstitutedcyclopen-1,3-ylene group; alternatively, a 2,4,5-trisubstitutedcyclopen-1,3-ylene group. In another non-limiting embodiment, L¹ can bea 2,6-disubstituted cyclohex-1,4-ylene group, a 2,3-disubstitutedcyclohex-1,4-ylene group, a 2,5-disubstituted cyclohex-1,4-ylene group,or a 2,3,5,6-tetrasubstituted cyclohex-1,4-ylene group. In someembodiments, L¹ can be a 2,6-disubstituted cyclohex-1,4-ylene group or a2,5-disubstituted cyclohex-1,4-ylene group; alternatively, a2,6-disubstituted cyclohex-1,4-ylene group; alternatively, a2,3-disubstituted cyclohex-1,4-ylene group; alternatively, a2,5-disubstituted cyclohex-1,4-ylene group; or alternatively, a2,3,5,6-tetrasubstituted cyclohex-1,4-ylene group. In yet anothernon-limiting embodiment, L¹ can be a 2-substituted cyclohex-1,3-ylenegroup, a 2,4-disubstituted cyclohex-1,3-ylene group, a 4,6-disubstitutedcyclohex-1,3-ylene group, or a 2,4,6-trisubstituted cyclohex-1,3-ylenegroup. In a further non-limiting embodiment, L¹ can be a 2-substitutedcyclohex-1,3-ylene group; alternatively, a 2,4-disubstitutedcyclohex-1,3-ylene group; alternatively, a 4,6-disubstitutedcyclohex-1,3-ylene group; or alternatively, a 2,4,6-trisubstitutedcyclohex-1,3-ylene group.

In an aspect, L¹ can be a bicyclylene group, a substituted bicyclylenegroup, a bis(cyclylene)methane group, a substitutedbis(cyclylene)methane group, a bis(cyclylene)ethane group, or asubstituted bis(cyclylene)ethane group; alternatively, a bicyclylenegroup, a bis(cyclylene)methane group, or a bis(cyclylene)ethane group;or alternatively, a substituted bicyclylene group, a substitutedbis(cyclylene)methane group, or a substituted bis(cyclylene)ethanegroup. In an embodiment, L¹ can be a bicyclylene group or a substitutedbicyclylene group; alternatively, a bis(cyclylene)methane group or asubstituted bis(cyclylene)methane group; or alternatively, abis(cyclylene)ethane group or a substituted bis(cyclylene)ethane group.In some embodiments, L¹ can be a bicyclylene group; alternatively, asubstituted bicyclylene group; alternatively, a bis(cyclylene)methanegroup; alternatively, a substituted bis(cyclylene)methane group;alternatively, a bis(cyclylene)ethane group; or alternatively, asubstituted bis(cyclylene)ethane group. Generally, anybis(cyclylene)ethane group disclosed herein (substituted orunsubstituted) can be a bis-1,1-(cyclylene)ethane group or abis-1,2-(cyclylene)ethane group; alternatively, abis-1,1-(cyclylene)ethane group; or alternatively, abis-1,2-(cyclylene)ethane group.

In an aspect, L¹ can be a bicyclohexylene group, a substitutedbicyclohexylene group, a bis(cyclohexylene)methane group, a substitutedbis(cyclohexylene)methane group, a bis(cyclohexylene)ethane group, or asubstituted bis(cyclohexylene)ethane group; alternatively, abicyclohexylene group, a bis(cyclohexylene)methane group, or abis(cyclohexylene)ethane group; or alternatively, a substitutedbicyclohexylene group, a substituted bis(cyclohexylene)methane group, ora substituted bis(cyclohexylene)ethane group. In an embodiment, L¹ canbe a bicyclohexylene group or a substituted bicyclohexylene group;alternatively, a bis(cyclohexylene)methane group or a substitutedbis(cyclohexylene)methane group; or alternatively, abis(cyclohexylene)ethane group or a substituted bis(cyclohexylene)ethanegroup. In some embodiments, L¹ can be a bicyclohexylene group;alternatively, a substituted bicyclohexylene group; alternatively, abis(cyclohexylene)methane group; alternatively, a substitutedbis(cyclohexylene)methane group; alternatively, abis(cyclohexylene)ethane group; or alternatively, a substitutedbis(cyclohexylene)ethane group. Generally, any bis(cyclohexylene)ethanegroup disclosed herein (substituted or unsubstituted) can be abis-1,1-(cyclohexylene)ethane group or a bis-1,2-(cyclohexylene)ethanegroup; alternatively, a bis-1,1-(cyclohexylene)ethane group; oralternatively, a bis-1,2-(cyclohexylene)ethane group.

In an embodiment, L¹ can be a bicyclohex-4,4′-ylene group, a3,3′-disubstituted bicyclohex-4,4′-ylene group, a3,3′,5,5′-tetrasubstitutedbicyclohex-4,4′-ylene group, abis(cyclohex-4-ylene) group, a bis(3-substitutedcyclohex-4-ylene)methane group, a bis(3,5-disubstitutedcyclohex-4-ylene)methane group, a bis-1,2-(cyclohex-4-ylene)ethanegroup, a bis-1,2-(3-substituted cyclohex-4-ylene)ethane group, abis-1,2-(3,5-disubstituted cyclohex-4-ylene)ethane group. In someembodiments, L¹ can be a bicyclohex-4,4′-ylene group, 3,3′-disubstitutedbicyclohex-4,4′-ylene group or a3,3′,5,5′-tetrasubstitutedbicyclohex-4,4′-ylene group; alternatively, abis(cyclohex-4-ylene)methane group, a bis(3-substitutedcyclohex-4-ylene)methane group or a bis(3,5-disubstitutedcyclohex-4-ylene)methane group; alternatively, abis-1,2-(cyclohex-4-ylene)ethane group, a bis-1,2-(3-substitutedcyclohex-4-ylene)ethane group or a bis-1,2-(3,5-disubstitutedcyclohex-4-ylene)ethane group. In other embodiments, L¹ can be abicyclohex-4,4′-ylene group; alternatively, a 3,3′-disubstitutedbicyclohex-4,4′-ylene group; alternatively, a3,3′,5,5′-tetrasubstitutedbicyclohex-4,4′-ylene group; alternatively, abis(cyclohex-4-ylene)methane group; alternatively, a bis(3-substitutedcyclohex-4-ylene)methane group; alternatively, a bis(3,5-disubstitutedcyclohex-4-ylene)methane group; alternatively, abis-1,2-(cyclohex-4-ylene)ethane group; alternatively, abis-1,2-(3-substituted cyclohex-4-ylene)ethane group; or alternatively,a bis-1,2-(3,5-disubstituted cyclohex-4-ylene)ethane group.

In an aspect, L¹ can be a phenylene group or a substituted phenylenegroup. In an embodiment, L¹ can be a phenylene group; or alternatively,a substituted phenylene group. In some embodiments, L¹ can be aphen-1,2-ylene group or a substituted phen-1,2-ylene group;alternatively, a phen-1,2-ylene group; or alternatively, a substitutedphen-1,2-ylene group. In other embodiments, L¹ can be a phen-1,3-ylenegroup or a substituted phen-1,3-ylene group; alternatively, aphen-1,3-ylene group; or alternatively, a substituted phen-1,3-ylenegroup. In yet other embodiments, L¹ can be a phen-1,4-ylene group or asubstituted phen-1,4-ylene group; alternatively, a phen-1,4-ylene group;or alternatively, a substituted phen-1,4-ylene group. In furtherembodiments, L¹ can be a phen-1,2-ylene group, a phen-1,3-ylene group,or a phen-1,4-ylene group; alternatively, a phen-1,3-ylene group or aphen-1,4-ylene group. In other embodiments, L¹ can be a substitutedphen-1,2-ylene group, a substituted phen-1,3-ylene group, or asubstituted phen-1,4-ylene group; alternatively, a substitutedphen-1,3-ylene group or a substituted phen-1,4-ylene group.

In a non-limiting embodiment, L¹ can be a 2,6-disubstitutedphen-1,4-ylene group, a 2,3-disubstituted phen-1,4-ylene group, a2,5-disubstituted phen-1,4-ylene group, or a 2,3,5,6-tetrasubstitutedphen-1,4-ylene group. In some embodiments, L¹ can be a 2,6-disubstitutedphen-1,4-ylene group or a 2,5-disubstituted phen-1,4-ylene group;alternatively, a 2,6-disubstituted phen-1,4-ylene group; alternatively,a 2,3-disubstituted phen-1,4-ylene group; alternatively, a2,5-disubstituted phen-1,4-ylene group; or alternatively, a2,3,5,6-tetrasubstituted phen-1,4-ylene group. In yet anothernon-limiting embodiment, L¹ can be a 2-substituted phen-1,3-ylene group,a 2,4-disubstituted phen-1,3-ylene group, a 4,6-disubstitutedphen-1,3-ylene group, or a 2,4,6-trisubstituted phen-1,3-ylene group. Ina further non-limiting embodiment, L¹ can be a 2-substitutedphen-1,3-ylene group; alternatively, a 2,4-disubstituted phen-1,3-ylenegroup; alternatively, a 4,6-disubstituted phen-1,3-ylene group; oralternatively, a 2,4,6-trisubstituted phen-1,3-ylene group.

In an aspect, L¹ can be a naphthylene group or a substituted naphthylenegroup. In an embodiment, L¹ can be a naphthylene group; oralternatively, a substituted naphthylene group. In some embodiments, L¹can be a naphth-1,3-ylene group, a substituted naphth-1,3-ylene group, anaphth-1,4-ylene group, a substituted naphth-1,4-ylene group, anaphth-1,5-ylene group, a substituted naphth-1,5-ylene group, anaphth-1,6-ylene group, a substituted naphth-1,6-ylene group, anaphth-1,7-ylene group, a substituted naphth-1,7-ylene group, anaphth-1,8-ylene group, or a substituted naphth-1,8-ylene group. Inother embodiments, L¹ can be a naphth-1,3-ylene group or a substitutednaphth-1,3-ylene group; alternatively, a naphth-1,4-ylene group or asubstituted naphth-1,4-ylene group; alternatively, a naphth-1,5-ylenegroup or a substituted naphth-1,5-ylene group; alternatively, anaphth-1,6-ylene group or a substituted naphth-1,6-ylene group;alternatively, a naphth-1,7-ylene group or a substitutednaphth-1,7-ylene group; or alternatively, a naphth-1,8-ylene group or asubstituted naphth-1,8-ylene group. In yet other embodiments, L¹ can bea naphth-1,3-ylene group; alternatively, a substituted naphth-1,3-ylenegroup; alternatively, a naphth-1,4-ylene group; alternatively, asubstituted naphth-1,4-ylene group; alternatively, a naphth-1,5-ylenegroup; alternatively, a substituted naphth-1,5-ylene group;alternatively, a naphth-1,6-ylene group; alternatively, a substitutednaphth-1,6-ylene group; alternatively, a naphth-1,7-ylene group;alternatively, a substituted naphth-1,7-ylene group; alternatively, anaphth-1,8-ylene group; or alternatively, a substituted naphth-1,8-ylenegroup.

In an aspect, L¹ can be a biphenylene group, a substituted biphenylenegroup, a bis(phenylene)methane group, a substitutedbis(phenylene)methane group, a bis(phenylene)ethane group, or asubstituted bis(phenylene)ethane group; alternatively, a biphenylenegroup, a bis(phenylene)methane group, or a bis(phenylene)ethane group;or alternatively, a substituted biphenylene group, a substitutedbis(phenylene)methane group, or a substituted bis(phenylene)ethanegroup. In an embodiment, L¹ can be a biphenylene group or a substitutedbiphenylene group; alternatively, bis(phenylene)methane group or asubstituted bis(phenylene)methane group; or alternatively, abis(phenylene)ethane group or a substituted bis(phenylene)ethane group.In some embodiments, L¹ can be a biphenylene group; alternatively, asubstituted biphenylene group; alternatively, a bis(phenylene)methanegroup; alternatively, a substituted bis(phenylene)methane group;alternatively, a bis(phenylene)ethane group; or alternatively, asubstituted bis(phenylene)ethane group. Generally, anybis(phenylene)ethane group disclosed herein (substituted orunsubstituted) can be a bis-1,1-(phenylene)ethane group or abis-1,2-(phenylene)ethane group; alternatively, abis-1,1-(phenylene)ethane group; or alternatively, abis-1,2-(phenylene)ethane group.

In an embodiment, L¹ can be a biphen-2-ylene group, a substitutedbiphen-2-ylene group, a biphen-3-ylene group, a substitutedbiphen-3-ylene group, a biphen-4-ylene group, or a substitutedbiphen-4-ylene group; or alternatively, a biphen-3-ylene group, asubstituted biphen-3-ylene group, a biphen-4-ylene group, or asubstituted biphen-4-ylene group. In some embodiments, L¹ can be abiphen-2-ylene group or a substituted biphen-2-ylene group;alternatively, a biphen-3-ylene group or a substituted biphen-3-ylenegroup; or alternatively, a biphen-4-ylene group or a substitutedbiphen-4-ylene group. In other embodiments, L¹ can be a biphen-2-ylenegroup; alternatively, a substituted biphen-2-ylene group; alternatively,a biphen-3-ylene group; alternatively, a substituted biphen-3-ylenegroup; alternatively, biphen-4-ylene group; or alternatively, asubstituted biphen-4-ylene group.

In an embodiment, L¹ can be a bis(phen-2-ylene)methane group, asubstituted bis(phen-2-ylene)methane group, a bis(phen-3-ylene)methanegroup, a substituted bis(phen-3-ylene)methane group, abis(phen-4-ylene)methane group, or a substitutedbis(phen-4-ylene)methane group; or alternatively, abis(phen-3-ylene)methane group, a substituted bis(phen-3-ylene)methanegroup, a bis(phen-4-ylene)methane group, or a substitutedbis(phen-4-ylene)methane group. In some embodiments, L¹ can be abis(phen-2-ylene)methane group or a substituted bis(phen-2-ylene)methanegroup; alternatively, a bis(phen-3-ylene)methane group or a substitutedbis(phen-3-ylene)methane group; or alternatively, abis(phen-4-ylene)methane group or a substituted bis(phen-4-ylene)methanegroup. In other embodiments, L¹ can be a bis(phen-2-ylene)methane group;alternatively, a substituted bis(phen-2-ylene)methane group;alternatively, a bis(phen-3-ylene)methane group; alternatively, asubstituted bis(phen-3-ylene)methane group; alternatively, abis(phen-4-ylene)methane group; or alternatively, a substitutedbis(phen-4-ylene)methane group.

In an embodiment, L¹ can be a bis(phen-2-ylene)ethane group, asubstituted bis(phen-2-ylene)ethane group, a bis(phen-3-ylene)ethanegroup, a substituted bis(phen-3-ylene)ethane group, abis(phen-4-ylene)ethane group, or a substituted bis(phen-4-ylene)ethanegroup; or alternatively, a bis(phen-3-ylene)ethane group, a substitutedbis(phen-3-ylene)ethane group, a bis(phen-4-ylene)ethane group, or asubstituted bis(phen-4-ylene)ethane group. In some embodiments, L¹ canbe a bis(phen-2-ylene)ethane group or a substitutedbis(phen-2-ylene)ethane group; alternatively, a bis(phen-3-ylene)ethanegroup or a substituted bis(phen-3-ylene)ethane group; or alternatively,a bis(phen-4-ylene)ethane group or a substituted bis(phen-4-ylene)ethanegroup. In other embodiments, L¹ can be a bis(phen-2-ylene)ethane group;alternatively, a substituted bis(phen-2-ylene)ethane group;alternatively, a bis(phen-3-ylene)ethane group; alternatively, asubstituted bis(phen-3-ylene)ethane group; alternatively, abis(phen-4-ylene)ethane group; or alternatively, a substitutedbis(phen-4-ylene)ethane group. Generally, any bis(phenylene)ethane groupdisclosed herein (substituted or unsubstituted) may be abis-1,1-(phenylene)ethane group or a bis-1,2-(phenylene)ethane group;alternatively, a bis-1,1-(phenylene)ethane group; or alternatively, abis-1,2-(phenylene)ethane group.

In an embodiment, L¹ can be a 3,3′-disubstituted biphen-4,4′-ylenegroup, a 3,3′,5,5′-tetrasubstitutedbiphen-4,4′-ylene group, abis(3-substituted phen-4-ylene)methane group, a bis(3,5-disubstitutedphen-4-ylene)methane group, a bis-1,2-(3-substituted phen-4-ylene)ethanegroup, a bis-1,2-(3,5-disubstituted phen-4-ylene)ethane group. In someembodiments, L¹ can be a 3,3′-disubstituted biphen-4,4′-ylene group or a3,3′,5,5′-tetrasubstitutedbiphen-4,4′-ylene group; alternatively, abis(3-substituted phen-4-ylene)methane group or a bis(3,5-disubstitutedphen-4-ylene)methane group; alternatively, a bis-1,2-(3-substitutedphen-4-ylene)ethane group or a bis-1,2-(3,5-disubstitutedphen-4-ylene)ethane group. In other embodiments, L¹ can be a3,3′-disubstituted biphen-4,4′-ylene group; alternatively,3,3′,5,5′-tetrasubstitutedbiphen-4,4′-ylene group; alternatively, abis(3-substituted phen-4-ylene)methane group; alternatively, abis(3,5-disubstituted phen-4-ylene)methane group; alternatively, abis-1,2-(3-substituted phen-4-ylene)ethane group; or alternatively, abis-1,2-(3,5-disubstituted phen-4-ylene)ethane group.

In an embodiment, L¹ can be a di(methylene)cycloalkane group or asubstituted di(methylene)cycloalkane group; alternatively, adi(methylene)cycloalkane group. The cycloalkane group of thedi(methylene)cycloalkane group can be cyclobutane group, a substitutedcyclobutane group, a cyclopentane group, a substituted cyclopentanegroup, a cyclohexane group, a substituted cyclohexane group, acycloheptane group, a substituted cycloheptane group, a cyclooctanegroup, or a substituted cyclooctane group; alternatively, a cyclopentanegroup, a substituted cyclopentane group, a cyclohexane group, or asubstituted cyclohexane group; alternatively, a cyclobutane group or asubstituted cyclobutane group; alternatively, a cyclopentane group or asubstituted cyclopentane group; alternatively, a cyclohexane group or asubstituted cyclohexane group; alternatively, a cycloheptane group or asubstituted cycloheptane group; or alternatively, a cyclooctane group,or a substituted cyclooctane group. In some embodiments, the cycloalkanegroup of the di(methylene)cycloalkane group can be cyclobutane group, acyclopentane group, a cyclohexane group, a cycloheptane group or acyclooctane group; or alternatively, a cyclopentane group or acyclohexane group. In other embodiments, the cycloalkane group of thedi(methylene)cycloalkane group can be cyclopentane group; alternatively,a substituted cyclopentane group; a cyclohexane group; or alternatively,a substituted cyclohexane group.

In an embodiment, L¹ can be a 1,3-di(methylene)cyclopentane group, asubstituted 1,3-di(methylene)cyclopentane group, a1,3-di(methylene)cyclohexane group, a substituted1,3-di(methylene)cyclohexane group, a 1,4-di(methylene)cyclohexanegroup, or a substituted 1,4-di(methylene)cyclohexane group;alternatively, 1,3-di(methylene)cyclopentane group, a1,3-di(methylene)cyclohexane group, or a 1,4-di(methylene)cyclohexanegroup. In some embodiments, L¹ can be a 1,3-di(methylene)cyclopentanegroup or a substituted 1,3-di(methylene)cyclopentane group;alternatively, a 1,3-di(methylene)cyclohexane group, a substituted1,3-di(methylene)cyclohexane group, a 1,4-di(methylene)cyclohexanegroup, or a substituted 1,4-di(methylene)cyclohexane group;alternatively, a 1,3-di(methylene)cyclohexane group or a substituted1,3-di(methylene)cyclohexane group; alternatively, a1,4-di(methylene)cyclohexane group or a substituted1,4-di(methylene)cyclohexane group; alternatively,1,3-di(methylene)cyclopentane group; alternatively, a1,3-di(methylene)cyclohexane group; or alternatively, a1,4-di(methylene)cyclohexane group.

In an aspect, L¹ can be a di(methylene)benzene group or a substituteddi(methylene)benzene group; alternatively, a di(methylene) benzenegroup. In an embodiment, L¹ can be a 1,2-di(methylene)benzene group, asubstituted 1,2-di(methylene)benzene group, a 1,3-di(methylene)benzenegroup, a substituted 1,3-di(methylene)benzene group, a1,4-di(methylene)benzene group, or a substituted1,4-di(methylene)benzene group; alternatively, a1,2-di(methylene)benzene group, a 1,3-di(methylene)benzene group, or a1,4-di(methylene)benzene group. In some embodiments, L¹ can be a1,2-di(methylene)benzene group or a substituted 1,2-di(methylene)benzenegroup; alternatively, a 1,3-di(methylene)benzene group or a substituted1,3-di(methylene)benzene group; alternatively, a1,4-di(methylene)benzene group or a substituted 1,4-di(methylene)benzenegroup; alternatively, a 1,2-di(methylene)benzene group; alternatively, a1,3-di(methylene)benzene group; or alternatively, a1,4-di(methylene)benzene group.

In an embodiment, each substituent for any substituted L¹ group (generalor specific) independently can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituent for any substituted L¹ group (general or specific)independently can be a halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, an alkylgroup or an alkoxy group; alternatively, a halogen; alternatively, analkyl group; or alternatively, alkoxy group. Halogens, hydrocarbylgroups, hydrocarboxy groups, alkyl group, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe a substituted L¹ group.

In an aspect, L¹ can have any Structure in Table 1. In an embodiment, L¹can have Structure 1L, 2L, 3L, 4L, 5L, 6L, or 7L; or alternatively, 8L,9L, 10L, 11L, 12L, 13L, or 14L. In some embodiments, L¹ can haveStructure 1L, 2L, or 3L; alternatively, Structure 4L, 5L, 6L, or 7L;alternatively, Structure 8L, 9L, or 10L; or alternatively, Structure11L, 12L, 13L, or 14L. In other embodiments, L¹ can have Structure 2L or3L; alternatively, Structure 9L or 10L; alternatively, Structure 4L or5L; alternatively, Structure 6L or 7L; or alternatively, Structure 11Lor 12L; or alternatively, Structure 13L or 14L. In further embodiments,L¹ can have Structure 1L; alternatively, Structure 2L; alternatively,Structure 3L; alternatively, Structure 4L; alternatively, Structure 5L;alternatively, Structure 6L; alternatively, Structure 7L; alternatively,Structure 8L; alternatively, Structure 9L; alternatively, Structure 10L;alternatively, Structure 11L; alternatively, Structure 12L;alternatively, Structure 13L; or alternatively, Structure 14L.

TABLE 1 Linking groups, L¹ or L² for N²-phosphinyl amidine compoundshaving Structure NP2, NP3, NP4, or NP5.

Structure 1L

Structure 2L

Structure 3L

Structure 4L

Structure 5L

Structure 6L

Structure 7L

Structure 8L

Structure 9L

Structure 10L

Structure 11L

Structure 12L

Structure 13L

Structure 14L

In an embodiment, La within L¹ Structures 6L, 7L, 13L, or 14L can be—(CR^(L)R^(L))_(m)— where each R^(L) independently can be hydrogen, amethyl group, an ethyl group, a propyl group, an isopropyl group, or abutyl group and m can be an integer from 1 to 5. In an embodiment, Lawithin L¹ Structures 6L, 7L, 13L, or 14L can be—CR^(L)R^(L)(CH₂)_(n)CR^(L)R^(L)— where each R^(L) independently can behydrogen, a methyl group, an ethyl group, a propyl group, an isopropylgroup, or a butyl group and n can be an integer from 0 to 3. In someembodiments, each R^(L) independently can be hydrogen or a methyl group;alternatively, hydrogen. In other embodiments, La can be a methylenegroup (—CH₂—), an ethylene group (—CH₂CH₂—), a propylene group(—CH₂CH₂CH₂—), a —CH(CH₃)CH₂— group, —C(CH₃)₂— group, or a butylenegroup (—CH₂CH₂CH₂CH₂—). In some non-limiting embodiments, La can be amethylene group (—CH₂—), an ethylene group (—CH₂CH₂—) or a —CH(CH₃)CH₂—group; or alternatively, an ethylene group (—CH₂CH₂—), or a —CH(CH₃)CH₂—group. In yet other embodiments, La can be a methylene group;alternatively, an ethylene group; alternatively, a propylene group;alternatively, a —CH(CH₃)CH₂— group; or alternatively, —C(CH₃)₂— group.

Generally, within L¹ Structures 1L, 2L, 3L, 4L, 5L, 6L, 7L, 8L, 9L, 10L,11L, 12L, 13L, or 14L, R^(1L)—R^(11L), R^(21L), R^(31L), R^(21L′),R^(31L′), R^(41L), R^(51L), R^(41L′), R^(51L′), R^(62L), R^(66L),R^(72L), R^(76L), R^(72L′), R^(76L′), R^(82L), R^(86L),R^(82L′)—R^(86L′) (when present in a indicated structure) independentlycan be hydrogen, a halogen, a hydrocarbyl group, or a hydrocarboxygroup; alternatively, hydrogen, a halogen, or a hydrocarbyl group;alternatively, hydrogen, a halogen, or a hydrocarboxy group;alternatively, hydrogen, a hydrocarbyl group, or a hydrocarboxy group;alternatively, hydrogen or a halogen; alternatively, hydrogen orhydrocarbyl group; or alternatively, hydrogen or a hydrocarboxy group.In an embodiment, R^(1L)—R^(11L), R^(21L), R^(31L), R^(21L′), R^(31L′),R^(41L), R^(51L), R^(41L′), R^(51L′), R^(62L), R^(66L), R^(72L),R^(76L), R^(72L′), R^(76L′), R^(82L), R^(86L), R^(82L′), R^(86L′), whenpresent in any 1L-14L structure, independently can be hydrogen, ahalogen, an alkyl group, or an alkoxy group; alternatively, hydrogen, ahalogen, and an alkyl group; alternatively, hydrogen, a halogen, or analkoxy group; alternatively, hydrogen, an alkyl group, or an alkoxygroup; alternatively, hydrogen or a halogen; alternatively, hydrogen oran alkyl group; or alternatively, hydrogen or an alkoxy group. Halogens,hydrocarbyl groups, hydrocarboxy groups, alkyl group, and alkoxy groupsthat can be utilized as substituents are independently disclosed herein(e.g. as substituents for substituted R¹ groups) and can be utilizedwithout limitation to further describe L¹ having any 1L-14L structure.

In an aspect, L¹ can have a formula (or structure) wherein one or morecarbon atom attached to the N¹ nitrogen atom of the N²-phosphinylamidine group can be a tertiary carbon atom or a quaternary carbon atom;a tertiary carbon atom; or alternatively, a quaternary carbon atom. Inan embodiment, L¹ can have a formula (or structure) wherein each carbonatom attached to an N¹ nitrogen atom of the N²-phosphinyl amidine groupcan be a tertiary carbon atom or a quaternary carbon atom;alternatively, a tertiary carbon atom; or alternatively, a quaternarycarbon atom.

In an embodiment, when an N¹ nitrogen atom of the N²-phosphinyl amidinegroup is attached to a ring atom of a L¹ group (e.g., cycloalkylene,arylene, dicycloalkylene, dicycloalkylenemethylene, diarylene,diarylenemethylene, a L¹ having Structure 1L-14L, or any other L¹ groupdisclosed herein), the L¹ group can comprise at least one substituentlocated on a carbon atom adjacent to the ring carbon atom attached to N¹nitrogen atom of the N²-phosphinyl amidine group; or alternatively, theL¹ group can comprise at least one substituent at each carbon atomadjacent to the ring carbon atom attached to N¹ nitrogen atom of theN²-phosphinyl amidine group. In some embodiments, when the N¹ nitrogenatom of the N²-phosphinyl amidine group is attached to a ring atom of aL¹ group (e.g., cycloalkylene, arylene, dicycloalkylene,dicycloalkylenemethylene, diarylene, diarylenemethylene, a L¹ havingStructure 1L-14L, or any other L¹ group disclosed herein), the L¹ groupcan consist of one substituent located on a carbon atom adjacent to thering carbon atom attached to N¹ nitrogen atom of the N²-phosphinylamidine group. In some embodiments, when the N¹ nitrogen atom of theN²-phosphinyl amidine group is attached to a ring atom of a L¹ group(e.g., cycloalkylene, arylene, dicycloalkylene,dicycloalkylenemethylene, diarylene, diarylenemethylene, a L¹ havingStructure 1L-14L, or any other L¹ group disclosed herein), the L¹ groupcan comprise only one substituent located on carbon atom adjacent to thering carbon atom attached to N¹ nitrogen atom of the N²-phosphinylamidine group; or alternatively, the L¹ group can comprise, or consistof, only one substituent located on each carbon atom adjacent to thering carbon atom attached to N¹ nitrogen atom of the N²-phosphinylamidine group.

In a non-limiting embodiment, L¹ can be a phen-1,4-ylene group, a2,6-dimethylphen-1,4-ylene group, a 2,6-diethylphen-1,4-ylene group, a2,6-diisopropyl phen-1,4-ylene group, a 2,6-di-tert-butylphen-1,4-ylenegroup, a 2,5-dimethylphen-1,4-ylene group, a 2,5-diethylphen-1,4-ylenegroup, a 2,5-diisopropylphen-1,4-ylene group, a2,5-di-tert-butylphen-1,4-ylene group, or a2,3,5,6-tetramethylphen-1,4-ylene group. In other non-limitingembodiments, L¹ can be a phen-1,4-ylene group, a2,6-dimethylphen-1,4-ylene group, a 2,6-diethylphen-1,4-ylene group, a2,6-diisopropyl phen-1,4-ylene group, or a2,6-di-tert-butylphen-1,4-ylene group; or alternatively, a2,5-dimethylphen-1,4-ylene group, a 2,5-diethylphen-1,4-ylene group, a2,5-diisopropylphen-1,4-ylene group, or a2,5-di-tert-butylphen-1,4-ylene group. In yet further non-limitingembodiments, L¹ can be a phen-1,4-ylene group; alternatively, a2,6-dimethylphen-1,4-ylene group; alternatively, a2,6-diethylphen-1,4-ylene group; alternatively, a 2,6-diisopropylphen-1,4-ylene group; alternatively, a 2,6-di-tert-butylphen-1,4-ylenegroup; alternatively, a 2,5-dimethylphen-1,4-ylene group; alternatively,a 2,5-diethylphen-1,4-ylene group; alternatively, a2,5-diisopropylphen-1,4-ylene group; alternatively, a2,5-di-tert-butylphen-1,4-ylene group; or alternatively, a2,3,5,6-tetramethylphen-1,4-ylene group.

In a non-limiting embodiment, L¹ can be a 3,3′-dimethylbiphen-4,4′-ylenegroup, 3,3′-diethylbiphen-4,4′-ylene group, a3,3′-diisopropylbiphen-4,4′-ylene group, a3,3′-di-tert-butylbiphen-4,4′-ylene group, a3,3′,5,5′-tetramethylbiphen-4,4′-ylene group,3,3′,5,5′-tetraethylbiphen-4,4′-ylene group, a3,3′,5,5′-tetraisopropylbiphen-4,4′-ylene group, or a3,3′,5,5′-tetra-tert-butylbiphen-4,4′-ylene group. In some embodiments,L¹ can be a 3,3′-dimethylbiphen-4,4′-ylene group,3,3′-diethylbiphen-4,4′-ylene group, a 3,3′-diisopropylbiphen-4,4′-ylenegroup, or a 3,3′-di-tert-butylbiphen-4,4′-ylene group; or alternatively,a 3,3′,5,5′-tetramethylbiphen-4,4′-ylene group,3,3′,5,5′-tetraethylbiphen-4,4′-ylene group, a3,3′,5,5′-tetraisopropylbiphen-4,4′-ylene group, or a3,3′,5,5′-tetra-tert-butylbiphen-4,4′-ylene group. In other embodiments,L¹ can be a 3,3′-dimethylbiphen-4,4′-ylene group; alternatively,3,3′-diethylbiphen-4,4′-ylene group; alternatively, a3,3′-diisopropylbiphen-4,4′-ylene group; alternatively, a3,3′-di-tert-butylbiphen-4,4′-ylene group; alternatively, a3,3′,5,5′-tetramethylbiphen-4,4′-ylene group; alternatively,3,3′,5,5′-tetraethylbiphen-4,4′-ylene group; alternatively, a3,3′,5,5′-tetraisopropylbiphen-4,4′-ylene group; or alternatively, a3,3′,5,5′-tetra-tert-butylbiphen-4,4′-ylene group.

In a non-limiting embodiment, L¹ can be abis(3-methylphen-4-ylene)methane group, abis(3-ethylphen-4-ylene)methane group, abis(3-isopropyphen-4-ylene)methane group, abis(3-tert-butylphen-4-ylene)methane group, abis(3,5-dimethylphen-4-ylene)methane group, abis(3,5-diethylphen-4-ylene)methane group, abis(3,5-diisopropyphen-4-ylene)methane group, or abis(3,5-di-tert-butylphen-4-ylene)methane group. In some embodiments, L¹can be a bis(3-methylphen-4-ylene)methane group, abis(3-ethylphen-4-ylene)methane group, abis(3-isopropyphen-4-ylene)methane group, abis(3-tert-butylphen-4-ylene)methane group; or alternatively, abis(3,5-dimethylphen-4-ylene)methane group, abis(3,5-diethylphen-4-ylene)methane group, abis(3,5-diisopropyphen-4-ylene)methane group, or abis(3,5-di-tert-butylphen-4-ylene)methane group. In other embodiments,L¹ can be a bis(3-methylphen-4-ylene)methane group; alternatively, abis(3-ethylphen-4-ylene)methane group; alternatively, abis(3-isopropyphen-4-ylene)methane group; alternatively, abis(3-tert-butylphen-4-ylene)methane group; alternatively, abis(3,5-dimethylphen-4-ylene)methane group; alternatively, abis(3,5-diethylphen-4-ylene)methane group; alternatively, abis(3,5-diisopropyphen-4-ylene)methane group; or alternatively, abis(3,5-di-tert-butylphen-4-ylene)methane group.

In a non-limiting embodiment, L¹ can be abis(3-methylphen-4-ylene)ethane group, a bis(3-ethylphen-4-ylene)ethanegroup, a bis(3-isopropylphen-4-ylene)ethane group, abis(3-tert-butylphen-4-ylene)ethane group abis(3,5-dimethylphen-4-ylene)ethane group, abis(3,5-diethylphen-4-ylene)ethane group, abis(3,5-diisopropylphen-4-ylene)ethane group, or abis(3,5-di-tert-butylphen-4-ylene)ethane group. In some embodiments, L¹can be a bis(3-methylphen-4-ylene)ethane group, abis(3-ethylphen-4-ylene)ethane group, abis(3-isopropylphen-4-ylene)ethane group, abis(3-tert-butylphen-4-ylene)ethane group; or alternatively, abis(3,5-dimethylphen-4-ylene)ethane group, abis(3,5-diethylphen-4-ylene)ethane group, abis(3,5-diisopropylphen-4-ylene)ethane group, or abis(3,5-di-tert-butylphen-4-ylene)ethane group. In other embodiments, L¹can be a bis(3-methylphen-4-ylene)ethane group; alternatively, abis(3-ethylphen-4-ylene)ethane group; alternatively, abis(3-isopropylphen-4-ylene)ethane group; alternatively, abis(3-tert-butylphen-4-ylene)ethane group; alternatively, abis(3,5-dimethylphen-4-ylene)ethane group; alternatively, abis(3,5-diethylphen-4-ylene)ethane group; alternatively, abis(3,5-diisopropylphen-4-ylene)ethane group; or alternatively, abis(3,5-di-tert-butylphen-4-ylene)ethane group.

Generally, D² can be an r valent organic group; alternatively, an an rvalent organic group consisting essentially of inert functional groups;or alternatively, an r valent hydrocarbon group. In an aspect, D² can bean r valent C₁ to C₃₀ organic group; alternatively, an r valent C₁ toC₂₀ organic group; alternatively, an r valent C₁ to C₁₅ organic group;alternatively, an r valent C₁ to C₁₀ organic group; or alternatively, anr valent C₁ to C₅ organic group. In another aspect, D² can be an rvalent C₁ to C₃₀ organic group consisting essentially of inertfunctional groups; alternatively, an r valent C₁ to C₂₀ organic groupconsisting essentially of inert functional groups; alternatively, an rvalent C₁ to C₁₅ organic group consisting essentially of inertfunctional groups; alternatively, an r valent C₁ to C₁₀ organic groupconsisting essentially of inert functional groups; or alternatively, anr valent C₁ to C₅ organic group consisting essentially of inertfunctional groups. In yet another aspect, D² can be an r valent C₁ toC₃₀ hydrocarbyl group; alternatively, an r valent C₁ to C₂₀ hydrocarbylgroup; alternatively, an r valent C₁ to C₁₅ hydrocarbyl group;alternatively, an r valent C₁ to C₁₀ hydrocarbyl group; oralternatively, an r valent C₁ to C₅ hydrocarbyl group. In yet otherembodiments, D² can be an r valent C₃ to C₃₀ aromatic group;alternatively, an r valent C₃ to C₂₀ aromatic group; alternatively, an rvalent C₃ to C₁₅ aromatic group; or alternatively, an r valent C₃ to C₁₀aromatic group.

In an aspect, r can be an integer greater than zero. In someembodiments, r can be an integer from 1 to 5; alternatively, an integerfrom 1 to 4; or alternatively, 2 or 3. In other embodiments, r can be 1;alternatively, 2; alternatively, 3; alternatively, 4; or alternatively,5.

In an aspect, L² can be a C₁ to C₃₀ organylene group; alternatively, aC₁ to C₂₀ organylene group; alternatively, a C₁ to C₁₅ organylene group;alternatively, a C₁ to C₁₀ organylene group; or alternatively, a C₁ toC₅ organylene group. In another aspect, L² can be a C₁ to C₃₀ organylenegroup consisting essentially of inert functional groups; alternatively,a C₁ to C₂₀ organylene group consisting essentially of inert functionalgroups; alternatively, a C₁ to C₁₅ organylene group consistingessentially of inert functional groups; alternatively, a C₁ to C₁₀organylene group; or alternatively, a C₁ to C₅ organylene groupconsisting essentially of inert functional groups. In yet anotheraspect, L² can be a C₁ to C₃₀ hydrocarbylene group; alternatively, a C₁to C₂₀ hydrocarbylene group; alternatively, a C₁ to C₁₅ hydrocarbylenegroup; alternatively, a C₁ to C₁₀ hydrocarbylene group; oralternatively, a C₁ to C₅ hydrocarbylene group. In yet otherembodiments, L² can be a C₃ to C₃₀ aromatic group; alternatively, a C₃to C₂₀ aromatic group; alternatively, a C₃ to C₁₅ aromatic group; oralternatively, a C₃ to C₁₀ aromatic group.

In an aspect, L² can be a C₁ to C₃₀ alkylene group, a C₄ to C₃₀cycloalkylene group, a C₄ to C₃₀ substituted cycloalkylene group, a C₃to C₃₀ aliphatic heterocyclylene group, a C₃ to C₃₀ substitutedaliphatic heterocyclylene group, a C₆ to C₃₀ arylene group, a C₆ to C₃₀substituted arylene group, a C₃ to C₃₀ heteroarylene group, or a C₃ toC₃₀ substituted heteroarylene group; alternatively, a C₁ to C₃₀ alkylenegroup, a C₄ to C₃₀ cycloalkylene group, a C₄ to C₃₀ substitutedcycloalkylene group, a C₆ to C₃₀ arylene group, or a C₆ to C₃₀substituted arylene group; alternatively, a C₄ to C₃₀ cycloalkylenegroup or a C₄ to C₃₀ substituted cycloalkylene group; alternatively, aC₃ to C₃₀ aliphatic heterocyclylene group or a C₃ to C₃₀ substitutedaliphatic heterocyclylene group; alternatively, a C₆ to C₃₀ arylenegroup or a C₆ to C₃₀ substituted arylene group; alternatively, a C₃ toC₃₀ heteroarylene group or a C₃ to C₃₀ substituted heteroarylene group;alternatively, a C₁ to C₃₀ alkylene group; alternatively, a C₄ to C₃₀cycloalkylene group; alternatively, a C₄ to C₃₀ substitutedcycloalkylene group; alternatively, a C₃ to C₃₀ aliphaticheterocyclylene group; alternatively, a C₃ to C₃₀ substituted aliphaticheterocyclylene group; alternatively, a C₆ to C₃₀ arylene group;alternatively, a C₆ to C₃₀ substituted arylene group; alternatively, aC₃ to C₃₀ heteroarylene group; or alternatively, a C₃ to C₃₀ substitutedheteroarylene group. In an embodiment, L² can be a C₁ to C₁₅ alkylenegroup, a C₄ to C₂₀ cycloalkylene group, a C₄ to C₂₀ substitutedcycloalkylene group, a C₃ to C₂₀ aliphatic heterocyclylene group, a C₃to C₂₀ substituted aliphatic heterocyclylene group, a C₆ to C₂₀ arylenegroup, a C₆ to C₂₀ substituted arylene group, a C₃ to C₂₀ heteroarylenegroup, or a C₃ to C₂₀ substituted heteroarylene group; alternatively, aC₁ to C₁₅ alkylene group, a C₄ to C₂₀ cycloalkylene group, a C₄ to C₂₀substituted cycloalkylene group, a C₆ to C₂₀ arylene group, or a C₆ toC₂₀ substituted arylene group; alternatively, a C₄ to C₂₀ cycloalkylenegroup or a C₄ to C₂₀ substituted cycloalkylene group; alternatively, aC₃ to C₂₀ aliphatic heterocyclylene group or a C₃ to C₂₀ substitutedaliphatic heterocyclylene group; alternatively, a C₆ to C₂₀ arylenegroup or a C₆ to C₂₀ substituted arylene group; alternatively, a C₃ toC₂₀ heteroarylene group or a C₃ to C₂₀ substituted heteroarylene group;alternatively, a C₁ to C₁₅ alkylene group; alternatively, a C₄ to C₂₀cycloalkylene group; alternatively, a C₄ to C₂₀ substitutedcycloalkylene group; alternatively, a C₃ to C₂₀ aliphaticheterocyclylene group; alternatively, a C₃ to C₂₀ substituted aliphaticheterocyclylene group; alternatively, a C₆ to C₂₀ arylene group;alternatively, a C₆ to C₂₀ substituted arylene group; alternatively, aC₃ to C₂₀ heteroarylene group; or alternatively, a C₃ to C₂₀ substitutedheteroarylene group. In other embodiments, L² can be a C₁ to C₁₀alkylene group, a C₄ to C₁₅ cycloalkylene group, a C₄ to C₁₅ substitutedcycloalkylene group, a C₃ to C₁₅ aliphatic heterocyclylene group, a C₃to C₁₅ substituted aliphatic heterocyclylene group, a C₆ to C₁₅ arylenegroup, a C₆ to C₁₅ substituted arylene group, a C₃ to C₁₅ heteroarylenegroup, or a C₃ to C₁₅ substituted heteroarylene group; alternatively, aC₁ to C₁₀ alkylene group, a C₄ to C₁₅ cycloalkylene group, a C₄ to C₁₅substituted cycloalkylene group, a C₆ to C₁₅ arylene group, or a C₆ toC₁₅ substituted arylene group; alternatively, a C₄ to C₁₅ cycloalkylenegroup or a C₄ to C₁₅ substituted cycloalkylene group; alternatively, aC₃ to C₁₅ aliphatic heterocyclylene group or a C₃ to C₁₅ substitutedaliphatic heterocyclylene group; alternatively, a C₆ to C₁₅ arylenegroup or a C₆ to C₁₅ substituted arylene group; alternatively, a C₃ toC₁₅ heteroarylene group or a C₃ to C₁₅ substituted heteroarylene group;alternatively, a C₁ to C₁₀ alkylene group; alternatively, a C₄ to C₁₅cycloalkylene group; alternatively, a C₄ to C₁₅ substitutedcycloalkylene group; alternatively, a C₃ to C₁₅ aliphaticheterocyclylene group; alternatively, a C₃ to C₁₅ substituted aliphaticheterocyclylene group; alternatively, a C₆ to C₁₅ arylene group;alternatively, a C₆ to C₁₅ substituted arylene group; alternatively, aC₃ to C₁₅ heteroarylene group; or alternatively, a C₃ to C₁₅ substitutedheteroarylene group. In further embodiments, L² can be a C₁ to C₅alkylene group.

In an embodiment, L² be a bond, a methylene group, an ethylene group, apropylene group, a butylene group, a pentylene group, a hexylene group,a heptylene group, an octylene group, a nonylene group, a decylenegroup, a undecylene group, a dodecylene group, a tridecylene group, atetradecylene group, a pentadecylene group, a hexadecylene group, aheptadecylene group, an octadecylene group, or a nonadecylene group; oralternatively, a methylene group, an ethylene group, a propylene group,a butylene group, a pentylene group, a hexylene group, a heptylenegroup, an octylene group, a nonylene group, a decylene group. In someembodiments, L² can be a methylene group, an ethylene group, a propylenegroup, a butylene group, or a pentylene group. In other embodiments, L²can be a bond; alternatively, a methylene group; alternatively, anethylene group; alternatively, a propylene group; alternatively, abutylene group; alternatively, a pentylene group; alternatively, ahexylene group; alternatively, a heptylene group; alternatively, anoctylene group; alternatively, a nonylene group; alternatively, adecylene group; alternatively, a undecylene group; alternatively, adodecylene group; alternatively, a tridecylene group; alternatively, atetradecylene group; alternatively, a pentadecylene group;alternatively, a hexadecylene group; alternatively, a heptadecylenegroup; alternatively, an octadecylene group; or alternatively, anonadecylene group. In some embodiments, L² can be a bond, a methylenegroup, an eth-1,2-ylene group, a prop-1,3-ylene group, a but-1,4-ylenegroup, a but-2,3-ylene group, a pent-1,5-ylene group, a2,2-dimethylprop-1,3-ylene group, a hex-1,6-ylene group, or a2,3-dimethylbut-2,3-ylene group; alternatively, an eth-1,2-ylene group,a prop-1,3-ylene group, a but-1,4-ylene group, a pent-1,5-ylene group,or a hex-1,6-ylene group; alternatively, a bond; alternatively, amethylene group; alternatively, an eth-1,2-ylene group; alternatively, aprop-1,3-ylene group; alternatively, a but-1,4-ylene group;alternatively, a but-2,3-ylene group; alternatively, a pent-1,5-ylenegroup; alternatively, a 2,2-dimethylprop-1,3-ylene group; alternatively,a hex-1,6-ylene group; or alternatively, a 2,3-dimethylbut-2,3-ylenegroup. In some embodiments, the alkylene groups which can be utilized asL² can be substituted. Each substituent of a substituted alkylene groupindependently can be a halogen or a hydrocarboxy group; alternatively, ahalogen; or alternatively, a hydrocarboxy group. Halogens andhydrocarboxy groups that can be utilized as substituents areindependently disclosed herein (e.g. as substituents for substituted R¹groups) and can be utilized without limitation to further describe thesubstituted alkylene group which can be utilized as L².

In an aspect, L² can have the formula—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)— wherein each R^(1a), R^(2a),R^(3a), and R^(4a) independently can be hydrogen, a halogen, a C₁ to C₅alkyl group, or a C₁ to C₅ alkoxy group and t can be zero or an integerranging from 1 to 28. In an embodiment, R^(1a), R^(2a), R^(3a), R^(4a)independently can be hydrogen, a halogen, or a C₁ to C₅ alkyl group;alternatively, hydrogen, a halogen, or a C₁ to C₅ alkoxy group;alternatively, hydrogen, a C₁ to C₅ alkyl group, or a C₁ to C₅ alkoxygroup; alternatively, hydrogen or a halogen; alternatively, hydrogen ora C₁ to C₅ alkyl group; alternatively, hydrogen or a C₁ to C₅ alkoxygroup; alternatively, hydrogen; or alternatively, a C₁ to C₅ alkylgroup. In an embodiment, t can be an integer ranging from 1 to 18;alternatively, 1 to 13; alternatively, 1 to 8; or alternatively, 1 to 3.In other embodiments, t can be zero. Halogens, C₁ to C₅ alkyl groups,and C₁ to C_(s) alkoxy groups that can be utilized as substituents areindependently described herein and can be utilized, without limitation,to further describe L² having the formula—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—. In another aspect, L² may havethe formula —(CH₂)_(s)— wherein s can be an integer ranging from 1 to30. In an embodiment, s can be an integer ranging from 1 to 20;alternatively, 1 to 15; alternatively, 1 to 10; or alternatively, 1 to5.

In an embodiment, L² can be a cyclobutylene group, a substitutedcyclobutylene group, a cyclopentylene group, a substitutedcyclopentylene group, a cyclohexylene group, a substituted cyclohexylenegroup, a cycloheptylene group, a substituted cycloheptylene group, acyclooctylene group, or a substituted cyclooctylene group. In someembodiments, a L² can be a cyclopentylene group, a substitutedcyclopentylene group, a cyclohexylene group, a substituted cyclohexylenegroup. In other embodiments, L² can be a cyclobutylene group or asubstituted cyclobutylene group; alternatively, a cyclopentylene groupor a substituted cyclopentylene group; alternatively, a cyclohexylenegroup or a substituted cyclohexylene group; alternatively, acycloheptylene group or a substituted cycloheptylene group; oralternatively, a cyclooctylene group, or a substituted cyclooctylenegroup. In further embodiments, L² can be a cyclopentylene group;alternatively, a substituted cyclopentylene group; a cyclohexylenegroup; or alternatively, a substituted cyclohexylene group.

In an embodiment, L² can be a cyclopent-1,3-ylene group, a substitutedcyclopent-1,3-ylene group, a cyclohex-1,3-ylene group, a substitutedcyclohex-1,3-ylene group, a cyclohex-1,4-ylene group, or a substitutedcyclohex-1,4-ylene group; alternatively, cyclopent-1,3-ylene group, acyclohex-1,3-ylene group, or a cyclohex-1,4-ylene group. In someembodiments, L² can be a cyclopent-1,3-ylene group, or a substitutedcyclopent-1,3-ylene group; alternatively, acyclohex-1,3-ylene group, asubstituted cyclohex-1,3-ylene group, a cyclohex-1,4-ylene group, or asubstituted cyclohex-1,4-ylene group; alternatively, acyclohex-1,3-ylene group or a substituted cyclohex-1,3-ylene group;alternatively, a cyclohex-1,4-ylene group or a substitutedcyclohex-1,4-ylene group; alternatively, a cyclopent-1,3-ylene group, acyclohex-1,3-ylene group, or a cyclohex-1,4-ylene group; oralternatively, a substituted cyclopent-1,3-ylene group, a substitutedcyclohex-1,3-ylene group, or a substituted cyclohex-1,4-ylene group. Inother embodiments, L¹ can be a cyclopent-1,3-ylene group; alternatively,a substituted cyclopent-1,3-ylene group; alternatively, acyclohex-1,3-ylene group; alternatively, a substitutedcyclohex-1,3-ylene group; alternatively, a cyclohex-1,4-ylene group; oralternatively, a substituted cyclohex-1,4-ylene group.

In an aspect, L² can be a bicyclylene group, a substituted bicyclylenegroup, a bis(cyclylene)methane group, a substitutedbis(cyclylene)methane group, a bis(cyclylene)ethane group, or asubstituted bis(cyclylene)ethane group; alternatively, a bicyclylenegroup, a bis(cyclylene)methane group, or a bis(cyclylene)ethane group;or alternatively, a substituted bicyclylene group, a substitutedbis(cyclylene)methane group, or a substituted bis(cyclylene)ethanegroup. In an embodiment, L² can be a bicyclylene group or a substitutedbicyclylene group; alternatively, a bis(cyclylene)methane group or asubstituted bis(cyclylene)methane group; or alternatively, abis(cyclylene)ethane group or a substituted bis(cyclylene)ethane group.In some embodiments, L² can be a bicyclylene group; alternatively, asubstituted bicyclylene group; alternatively, a bis(cyclylene)methanegroup; alternatively, a substituted bis(cyclylene)methane group;alternatively, a bis(cyclylene)ethane group; or alternatively, asubstituted bis(cyclylene)ethane group. Generally, anybis(cyclylene)ethane group disclosed herein (substituted orunsubstituted) can be a bis-1,1-(cyclylene)ethane group or abis-1,2-(cyclylene)ethane group; alternatively, abis-1,1-(cyclylene)ethane group; or alternatively, abis-1,2-(cyclylene)ethane group.

In an aspect, L² can be a bicyclohexylene group, a substitutedbicyclohexylene group, a bis(cyclohexylene)methane group, a substitutedbis(cyclohexylene)methane group, a bis(cyclohexylene)ethane group, or asubstituted bis(cyclohexylene)ethane group; alternatively, abicyclohexylene group, a bis(cyclohexylene)methane group, or abis(cyclohexylene)ethane group; or alternatively, a substitutedbicyclohexylene group, a substituted bis(cyclohexylene)methane group, ora substituted bis(cyclohexylene)ethane group. In an embodiment, L² canbe a bicyclohexylene group or a substituted bicyclohexylene group;alternatively, a bis(cyclohexylene)methane group or a substitutedbis(cyclohexylene)methane group; or alternatively, abis(cyclohexylene)ethane group or a substituted bis(cyclohexylene)ethanegroup. In some embodiments, L² can be a bicyclohexylene group;alternatively, a substituted bicyclohexylene group; alternatively, abis(cyclohexylene)methane group; alternatively, a substitutedbis(cyclohexylene)methane group; alternatively, abis(cyclohexylene)ethane group; or alternatively, a substitutedbis(cyclohexylene)ethane group. Generally, any bis(cyclohexylene)ethanegroup disclosed herein (substituted or unsubstituted) can be abis-1,1-(cyclohexylene)ethane group or a bis-1,2-(cyclohexylene)ethanegroup; alternatively, a bis-1,1-(cyclohexylene)ethane group; oralternatively, a bis-1,2-(cyclohexylene)ethane group.

In an embodiment, L² can be a bicyclohex-4,4′-ylene group, a3,3′-disubstituted bicyclohex-4,4′-ylene group, a3,3′,5,5′-tetrasubstitutedbicyclohex-4,4′-ylene group, abis(cyclohex-4-ylene) group, a bis(3-substitutedcyclohex-4-ylene)methane group, a bis(3,5-disubstitutedcyclohex-4-ylene)methane group, a bis-1,2-(cyclohex-4-ylene)ethanegroup, a bis-1,2-(3-substituted cyclohex-4-ylene)ethane group, or abis-1,2-(3,5-disubstituted cyclohex-4-ylene)ethane group. In someembodiments, L² can be a bicyclohex-4,4′-ylene group, 3,3′-disubstitutedbicyclohex-4,4′-ylene group or a3,3′,5,5′-tetrasubstitutedbicyclohex-4,4′-ylene group; alternatively, abis(cyclohex-4-ylene)methane group, a bis(3-substitutedcyclohex-4-ylene)methane group or a bis(3,5-disubstitutedcyclohex-4-ylene)methane group; or alternatively, abis-1,2-(cyclohex-4-ylene)ethane group, a bis-1,2-(3-substitutedcyclohex-4-ylene)ethane group or a bis-1,2-(3,5-disubstitutedcyclohex-4-ylene)ethane group. In other embodiments, L² can be abicyclohex-4,4′-ylene group; alternatively, a 3,3′-disubstitutedbicyclohex-4,4′-ylene group; alternatively, a3,3′,5,5′-tetrasubstitutedbicyclohex-4,4′-ylene group; alternatively, abis(cyclohex-4-ylene)methane group; alternatively, a bis(3-substitutedcyclohex-4-ylene)methane group; alternatively, a bis(3,5-disubstitutedcyclohex-4-ylene)methane group; alternatively, abis-1,2-(cyclohex-4-ylene)ethane group; alternatively, abis-1,2-(3-substituted cyclohex-4-ylene)ethane group; or alternatively,a bis-1,2-(3,5-disubstituted cyclohex-4-ylene)ethane group.

In an embodiment, L² can be a di(methylene)cycloalkane group or asubstituted di(methylene)cycloalkane group; or alternatively, adi(methylene)cycloalkane group. The cycloalkane group of thedi(methylene)cycloalkane group can be cyclobutane group, a substitutedcyclobutane group, a cyclopentane group, a substituted cyclopentanegroup, a cyclohexane group, a substituted cyclohexane group, acycloheptane group, a substituted cycloheptane group, a cyclooctanegroup, or a substituted cyclooctane group; alternatively, a cyclopentanegroup, a substituted cyclopentane group, a cyclohexane group, or asubstituted cyclohexane group; alternatively, a cyclobutane group or asubstituted cyclobutane group; alternatively, a cyclopentane group or asubstituted cyclopentane group; alternatively, a cyclohexane group or asubstituted cyclohexane group; alternatively, a cycloheptane group or asubstituted cycloheptane group; or alternatively, a cyclooctane group,or a substituted cyclooctane group. In some embodiments, the cycloalkanegroup of the di(methylene)cycloalkane group can be cyclobutane group, acyclopentane group, a cyclohexane group, a cycloheptane group, or acyclooctane group; or alternatively, a cyclopentane group or acyclohexane group. In other embodiments, the cycloalkane group of thedi(methylene)cycloalkane group can be cyclopentane group; alternatively,a substituted cyclopentane group; a cyclohexane group; or alternatively,a substituted cyclohexane group.

In an embodiment, L² can be a 1,3-di(methylene)cyclopentane group, asubstituted 1,3-di(methylene)cyclopentane group, a1,3-di(methylene)cyclohexane group, a substituted1,3-di(methylene)cyclohexane group, a 1,4-di(methylene)cyclohexanegroup, or a substituted 1,4-di(methylene)cyclohexane group; oralternatively, a 1,3-di(methylene)cyclopentane group, a1,3-di(methylene)cyclohexane group, or a 1,4-di(methylene)cyclohexanegroup. In some embodiments, L² can be a 1,3-di(methylene)cyclopentanegroup, a substituted 1,3-di(methylene)cyclopentane group; alternatively,a 1,3-di(methylene)cyclohexane group, a substituted1,3-di(methylene)cyclohexane group, a 1,4-di(methylene)cyclohexanegroup, or a substituted 1,4-di(methylene)cyclohexane group;alternatively, a 1,3-di(methylene)cyclohexane group, a substituted1,3-di(methylene)cyclohexane group; alternatively, a1,4-di(methylene)cyclohexane group, or a substituted1,4-di(methylene)cyclohexane group; alternatively,1,3-di(methylene)cyclopentane group; alternatively, a1,3-di(methylene)cyclohexane group; or alternatively, a1,4-di(methylene)cyclohexane group.

In an aspect, L² can be a phenylene group or a substituted phenylenegroup. In an embodiment, L² can be a phenylene group; or alternatively,a substituted phenylene group. In some embodiments, L² can be aphen-1,2-ylene group or a substituted phen-1,2-ylene group;alternatively, a phen-1,2-ylene group; or alternatively, a substitutedphen-1,2-ylene group. In other embodiments, L² can be a phen-1,3-ylenegroup or a substituted phen-1,3-ylene group; alternatively, aphen-1,3-ylene group; or alternatively, a substituted phen-1,3-ylenegroup. In yet other embodiments, L² can be a phen-1,4-ylene group or asubstituted phen-1,4-ylene group; alternatively, a phen-1,4-ylene group;or alternatively, a substituted phen-1,4-ylene group. In furtherembodiments, L² can be a phen-1,2-ylene group, a phen-1,3-ylene group,or a phen-1,4-ylene group; alternatively, a phen-1,3-ylene group or aphen-1,4-ylene group. In other embodiments, L² can be a substitutedphen-1,2-ylene group, a substituted phen-1,3-ylene group, or asubstituted phen-1,4-ylene group; alternatively, a substitutedphen-1,3-ylene group, or a substituted phen-1,4-ylene group.

In an aspect, L² can be a naphthylene group or a substituted naphthylenegroup. In an embodiment, L² can be a naphthylene group; oralternatively, a substituted naphthylene group. In some embodiments, L²can be a naphth-1,3-ylene group, a substituted naphth-1,3-ylene group, anaphth-1,4-ylene group, a substituted naphth-1,4-ylene group, anaphth-1,5-ylene group, a substituted naphth-1,5-ylene group, anaphth-1,6-ylene group, a substituted naphth-1,6-ylene group, anaphth-1,7-ylene group, a substituted naphth-1,7-ylene group, anaphth-1,8-ylene group, or a substituted naphth-1,8-ylene group. Inother embodiments, L² can be a naphth-1,3-ylene group or a substitutednaphth-1,3-ylene group; alternatively, a naphth-1,4-ylene group or asubstituted naphth-1,4-ylene group; alternatively, a naphth-1,5-ylenegroup or a substituted naphth-1,5-ylene group; alternatively, anaphth-1,6-ylene group or a substituted naphth-1,6-ylene group;alternatively, a naphth-1,7-ylene group or a substitutednaphth-1,7-ylene group; or alternatively, a naphth-1,8-ylene group or asubstituted naphth-1,8-ylene group. In yet other embodiments, L² can bea naphth-1,3-ylene group; alternatively, a substituted naphth-1,3-ylenegroup; alternatively, a naphth-1,4-ylene group; alternatively, asubstituted naphth-1,4-ylene group; alternatively, a naphth-1,5-ylenegroup; alternatively, a substituted naphth-1,5-ylene group;alternatively, a naphth-1,6-ylene group; alternatively, a substitutednaphth-1,6-ylene group; alternatively, a naphth-1,7-ylene group;alternatively, a substituted naphth-1,7-ylene group; alternatively, anaphth-1,8-ylene group; or alternatively, a substituted naphth-1,8-ylenegroup.

In an aspect, L² can be a biphenylene group, a substituted biphenylenegroup, a bis(phenylene)methane group, a substitutedbis(phenylene)methane group, a bis(phenylene)ethane group, or asubstituted bis(phenylene)ethane group; or alternatively, a biphenylenegroup, a bis(phenylene)methane group, or a bis(phenylene)ethane group;or alternatively, a substituted biphenylene group, a substitutedbis(phenylene)methane group, or a substituted bis(phenylene)ethanegroup. In an embodiment, L² can be a biphenylene group or a substitutedbiphenylene group; alternatively, bis(phenylene)methane group or asubstituted bis(phenylene)methane group; or alternatively, abis(phenylene)ethane group or a substituted bis(phenylene)ethane group.In some embodiments, L² can be a biphenylene group; alternatively, asubstituted biphenylene group; alternatively, a bis(phenylene)methanegroup; alternatively, a substituted bis(phenylene)methane group;alternatively, a bis(phenylene)ethane group; or alternatively, asubstituted bis(phenylene)ethane group. Generally, anybis(phenylene)ethane group disclosed herein (substituted orunsubstituted) can be a bis-1,1-(phenylene)ethane group or abis-1,2-(phenylene)ethane group; alternatively, abis-1,1-(phenylene)ethane group; or alternatively, abis-1,2-(phenylene)ethane group.

In an embodiment, L² can be a biphen-3-ylene group, a substitutedbiphen-3-ylene group, a biphen-4-ylene group, or a substitutedbiphen-4-ylene group. In some embodiments, L² can be a biphen-3-ylenegroup or a substituted biphen-3-ylene group; or alternatively, abiphen-4-ylene group or a substituted biphen-4-ylene group. In otherembodiments, L¹ can be a biphen-3-ylene group; alternatively, asubstituted biphen-3-ylene group; alternatively, a biphen-4-ylene group;or alternatively, a substituted biphen-4-ylene group.

In an embodiment, L² can be a bis(phen-3-ylene)methane group, asubstituted bis(phen-3-ylene)methane group, a bis(phen-4-ylene)methanegroup, or a substituted bis(phen-4-ylene)methane group. In someembodiments, L² can be a bis(phen-3-ylene)methane group or a substitutedbis(phen-3-ylene)methane group; or alternatively, abis(phen-4-ylene)methane group or a substituted bis(phen-4-ylene)methanegroup. In other embodiments, L² can be a bis(phen-3-ylene)methane group;alternatively, a substituted bis(phen-3-ylene)methane group;alternatively, a bis(phen-4-ylene)methane group; or alternatively, asubstituted bis(phen-4-ylene)methane group.

In an embodiment, L² can be a bis(phen-3-ylene)ethane group, asubstituted bis(phen-3-ylene)ethane group, a bis(phen-4-ylene)ethanegroup, or a substituted bis(phen-4-ylene)ethane group. In someembodiments, L² can be a bis(phen-3-ylene)ethane group or a substitutedbis(phen-3-ylene)ethane group; or alternatively, abis(phen-4-ylene)ethane group or a substituted bis(phen-4-ylene)ethanegroup. In other embodiments, L² can be a bis(phen-3-ylene)ethane group;alternatively, a substituted bis(phen-3-ylene)ethane group;alternatively, bis(phen-4-ylene)ethane group; or alternatively, asubstituted bis(phen-4-ylene)ethane group. Generally, anybis(phenylene)ethane group disclosed herein (substituted orunsubstituted) may be a bis-1,1-(phenylene)ethane group or abis-1,2-(phenylene)ethane group; alternatively, abis-1,1-(phenylene)ethane group; or alternatively, abis-1,2-(phenylene)ethane group.

In an aspect, L² can be a di(methylene)benzene group, or a substituteddi(methylene)benzene group; alternatively, a di(methylene) benzenegroup. In an embodiment, L² can be a 1,2-di(methylene)benzene group, asubstituted 1,2-di(methylene)benzene group, a 1,3-di(methylene)benzenegroup, a substituted 1,3-di(methylene)benzene group, a1,4-di(methylene)benzene group, or a substituted1,4-di(methylene)benzene group; alternatively, a1,2-di(methylene)benzene group, a 1,3-di(methylene)benzene group, or a1,4-di(methylene)benzene group. In some embodiments, L² can be a1,2-di(methylene)benzene group or a substituted 1,2-di(methylene)benzenegroup; alternatively, a 1,3-di(methylene)benzene group or a substituted1,3-di(methylene)benzene group; alternatively, a1,4-di(methylene)benzene group or a substituted 1,4-di(methylene)benzenegroup; alternatively, a 1,2-di(methylene)benzene group; alternatively, a1,3-di(methylene)benzene group; or alternatively, a1,4-di(methylene)benzene group.

In an embodiment, each substituent for any substituted L² group (generalor specific) independently can be a halogen, a hydrocarbyl group, or ahydrocarboxy group; alternatively, a halogen or a hydrocarbyl group;alternatively, a hydrocarbyl group or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. In some embodiments, eachsubstituent for any substituted L² group (general or specific)independently can be a halogen, an alkyl group, or an alkoxy group;alternatively, a halogen or an alkyl group; alternatively, an alkylgroup or an alkoxy group; alternatively, a halogen; alternatively, analkyl group; or alternatively, an alkoxy group. Halogens, hydrocarbylgroups, hydrocarboxy groups, alkyl group, and alkoxy groups that can beutilized as substituents are independently disclosed herein (e.g. assubstituents for substituted R¹ groups) and can be utilized withoutlimitation to further describe a substituted L² group.

In an embodiment, L² can have any Structure in Table 1. In anembodiment, L² can have Structure 1L, 2L, 3L, 4L, 5L, 6L, or 7L; oralternatively, 8L, 9L, 10L, 11L, 12L, 13L, or 14L. In some embodiments,L² can have Structure 1L, 2L, or 3L; alternatively, 4L, 5L, 6L, or 7L;alternatively, 8L, 9L, or 10L; or alternatively, 11L, 12L, 13L, or 14L.In other embodiments, L² can have Structure 2L or 3L; alternatively, 9L,or 10L; alternatively, 4L or 5L; alternatively, 6L or 7L; oralternatively, 11L or 12L; or alternatively, 13L or 14L. In furtherembodiments, L² can have Structure 1L; alternatively, 2L; alternatively,3L; alternatively, 4L; alternatively, 5L; alternatively, 6L;alternatively, 7L; alternatively, 8L; alternatively, 9L; alternatively,10L; alternatively, 11L; alternatively, 12L; alternatively, 13L; oralternatively, 14L. Generally, L² may have any embodiment of Structures1L-14L described herein. Generally, L² can have any aspect or embodimentof the Structures of Table 1 described for L¹.

In an aspect, the N²-phosphinyl amidine compound can comprise anN²-phosphinyl amidine group and a metal salt complexing group. Inanother aspect, the N²-phosphinyl amidine compound can comprise anN²-phosphinyl amidine group, a metal salt complexing group, and alinking group linking the metal salt complexing group to theN²-phosphinyl amidine group. In yet another aspect, the N²-phosphinylamidine compound can comprise an N²-phosphinyl amidine group, a metalsalt complexing group, and a linking group linking the metal saltcomplexing group to the N¹ nitrogen atom of the N²-phosphinyl amidinegroup. Generally, the N²-phosphinyl amidine group and the metal saltcomplexing group are independent elements of the N²-phosphinyl amidinecompound comprising an N²-phosphinyl amidine group and a metal saltcomplexing group. Consequently, the N²-phosphinyl amidine compoundcomprising an N²-phosphinyl amidine group and a metal salt complexinggroup can be described using any combination of the aspects andembodiments of the N²-phosphinyl amidine group described herein and themetal salt complexing group described herein. Additionally, the N²phosphinyl amidine group, the metal salt complexing group, and thelinking group linking the metal salt complexing group to theN²-phosphinyl amidine group (or the linking group linking the metal saltcomplexing group to the N¹ nitrogen atom of the N²-phosphinyl amidinegroup) are independent elements of the N²-phosphinyl amidine compoundcomprising an N²-phosphinyl amidine group, a metal salt complexinggroup, and a linking group liking the metal salt complexing group to theN²-phosphinyl amidine group. Thus, the N²-phosphinyl amidine compoundcomprising an N²-phosphinyl amidine group, a metal salt complexinggroup, and a linking group linking the metal salt complexing group tothe N²-phosphinyl amidine group (or the linking group linking the metalsalt complexing group to the N¹ nitrogen atom of the N²-phosphinylamidine group) can be described using any combination of the aspects andembodiments of the N²-phosphinyl amidine group described herein, themetal salt complexing group described herein, and linking groupdescribed herein.

In embodiments, the N²-phosphinyl amidine compound comprising anN²-phosphinyl amidine group, a metal salt complexing group, and alinking group linking the metal salt complexing group to theN²-phosphinyl amidine group can have Structure NP11, Structure NP13,Structure NP15, Structure NP16, Structure NP18, or Structure NP20;alternatively, Structure NP11, Structure NP13, or Structure NP15;alternatively, Structure NP16, Structure NP18, or Structure NP20;alternatively, Structure NP11; alternatively, Structure NP13;alternatively, Structure NP15; alternatively, Structure NP16;alternatively, Structure NP18; or alternatively, Structure NP20. R², R³,R⁴, R⁵, L², D, and r are independently described as features of theN²-phosphinyl amidine compounds described herein and can be utilizedwithout limitation to describe R², R³, R⁴, R⁵, L², D, and r in theN²-phosphinyl amidine compounds having Structure NP11, Structure NP13,Structure NP15, Structure NP16, Structure NP18, and/or Structure NP20.

The metal salt complexing group, Q¹, can be any group comprising aheteroatom capable of complexing with the metal salt. The linking group,L³, can be any group capable of linking the metal salt complexing groupto the N²-phosphinyl amidine group. In some embodiments, the linkinggroup includes all atoms between the N¹ nitrogen atom of theN²-phosphinyl amidine group, and the metal salt complexing group. If themetal salt complexing group is acyclic, the linking group includes allatoms between an atom of the N²-phosphinyl amidine group and theheteroatom of metal complexing group; or alternatively, between the N¹nitrogen atom of the N²-phosphinyl amidine group and the heteroatom ofthe metal salt complexing functional group. For example, inN¹-(2-(dimethylamino)ethyl)-N²-(diphenylphosphino) the linking group is—CH₂CH₂— and the metal salt complexing group is the N,N-dimethylaminylgroup, and in N¹-(2-(phenylthio)phenyl)-N²-(diisopropylphosphino) thelinking group is the phenyl-1,2-ene group and the metal salt complexinggroup is the phenylthio group. However, if the heteroatom of the metalsalt complexing group is contained within a ring or a ring system, thelinking group includes all the atoms between an atom of theN²-phosphinyl amidine group and the first atom of the ring or ringsystem containing the heteroatom of metal complexing group; oralternatively, between the N¹ nitrogen atom of the N²-phosphinyl amidinegroup and the first atom of the ring or ring system containing theheteroatom of metal complexing group. For example, inN¹-(2-(morpholin-1-yl)ethyl)-N²-(diisopropylphosphino) the linking groupis —CH₂CH₂— and the metal salt complexing group is the morpholin-1-ylgroup and in N¹-(thiazol-2-yl)-N²-(diphenylphosphino) the linking groupis a bond and the metal salt complexing group is the thiazol-2-yl group.

The metal salt complexing group, Q¹, can be any group comprising aheteroatom capable of complexing with the metal salt. In embodiments,the metal salt complexing group can be a C₁ to C₃₀ group comprising aheteroatom; alternatively, a C₁ to C₂₀ group comprising a heteroatom;alternatively, a C₁ to C₁₅ group comprising a heteroatom; alternatively,a C₁ to C₁₀ group comprising a heteroatom; or alternatively, a C₁ to C₅group comprising a heteroatom. In some embodiments, the metal saltcomplexing heteroatom of the metal salt complexing group can be oxygen,sulfur, nitrogen, or phosphorus. In other embodiments, the metal saltcomplexing heteroatom of the metal salt complexing group can be oxygenor sulfur. In yet other embodiments, the metal salt complexingheteroatom of the metal salt complexing group can be nitrogen, orphosphorus. In further embodiments, the metal salt complexing heteroatomof the metal salt complexing group can be oxygen; alternatively, sulfur;alternatively, nitrogen; or alternatively, phosphorus. Optionally, themetal salt complexing group can contain additional heteroatoms which donot complex the metal salt in an N²-phosphinyl amidine metal saltcomplex such as inert heteroatoms (e.g. halides, or silicon) and/oradditional metal salt complexing heteroatom(s) which do not complex withthe metal salt (e.g. because of the position in the non-complexing metalcomplexing group within the N²-phosphinyl amidine compound).

In an embodiment, the metal salt complexing group can be a dihydrocarbylaminyl group, a dihydrocarbyl phosphinyl group, a hydrocarbyl etherylgroup, or a hydrocarbyl sulfidyl group. In some embodiments, the metalsalt complexing group can be a dihydrocarbyl aminyl group;alternatively, a dihydrocarbyl phosphinyl group; alternatively, ahydrocarbyl etheryl group; or alternatively, a hydrocarbyl sulfidylgroup. In an embodiment, each hydrocarbyl group of the dihydrocarbylaminyl group, the dihydrocarbyl phosphinyl group, the hydrocarbyletheryl group, or a hydrocarbyl sulfidyl group utilized as a metal saltcomplexing group can be a C₁ to C₃₀ hydrocarbyl group; alternatively, aC₁ to C₂₀ hydrocarbyl group; alternatively, a C₁ to C₁₅ hydrocarbylgroup; alternatively, a C₁ to C₁₀ hydrocarbyl group; or alternatively, aC₁ to C₅ hydrocarbyl group. In some embodiments, each hydrocarbyl groupof the dihydrocarbyl aminyl group, the dihydrocarbyl phosphinyl group,the hydrocarbyl etheryl group, or a hydrocarbyl sulfidyl group utilizedas a metal salt complexing group can be an alkyl group, an cycloalkylgroup, an aryl group, or an aralkyl group; alternatively, an alkylgroup; alternatively, an cycloalkyl group; alternatively, an aryl group;or alternatively, an aralkyl group. Alkyl groups, cycloalkyl groups,aryl groups, and aralkyl groups are independently disclosed herein andmay be utilized without limitation to further describe the metal saltcomplexing group.

In some embodiments, the metal complexing group can be dialkyl aminylgroup, a dicycloalkyl aminyl group, a di(substituted cycloalkyl) aminylgroup), an N-(alkyl)-N-(cycloalkyl) aminyl group, anN-(alkyl)-N-(substituted cycloalkyl) aminyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) aminyl group, a diaryl aminylgroup, a di(substituted aryl) aminyl group, an N-aryl-N-(substitutedaryl) aminyl group, an N-alkyl-N-aryl aminyl group, anN-alkyl-N-(substituted aryl) aminyl group, a dialkyl phosphinyl group, adicycloalkyl phosphinyl group, a di(substituted cycloalkyl) phosphinylgroup), an N-(alkyl)-N-(cycloalkyl) phosphinyl group, anN-(alkyl)-N-(substituted cycloalkyl) phosphinyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) phosphinyl group, a diarylphosphinyl group, a di(substituted aryl) phosphinyl group, aP-aryl-P-(substituted aryl) phosphinyl group, a P-alkyl-P-arylphosphinyl group, a P-alkyl-P-(substituted aryl) phosphinyl group, analkyl etheryl group, an aryl etheryl group, a substituted aryl etherylgroup, an alkyl sulfidyl group, an aryl sulfidyl group, a substitutedaryl sulfidyl group, a furanyl group, a substituted furanyl group, athienyl group, a substituted thienyl group, a tetrahydrofuranyl group, asubstituted tetrahydrofuranyl group, a thiophanyl group, a substitutedthiophanyl group, a pyridinyl group, a substituted pyridinyl group, amorphilinyl group, a substituted morphilinyl group, a pyranyl group, asubstituted pyranyl group, a tetrahydropyranyl group, a substitutedtetrahydropyranyl group, a quinolinyl group, a substituted quinolinylgroup, a pyrrolyl group, a substituted pyrrolyl group, a pyrrolidinylgroup, a substituted pyrrolidinyl group, a piperidinyl group, or asubstituted piperidinyl group. In embodiments, the metal salt complexinggroup can be a dialkyl aminyl group, a dicycloalkyl aminyl group, adiaryl aminyl group, a dialkyl phosphinyl group, a dicycloalkylphosphinyl group, a diaryl phosphinyl group, an alkyl etheryl group, anaryl etheryl group, an alkyl sulfidyl group, an aryl sulfidyl group, afuranyl group, a thienyl group, a tetrahydrofuranyl group, a thiophanylgroup, a pyridinyl group, a morphilinyl group, a pyranyl group, atetrahydropyranyl group, a quinolinyl group, a pyrrolyl group, apyrrolidinyl group, or a piperidinyl group. In some embodiments, themetal salt complexing group can be a dialkyl aminyl group, adicycloalkyl aminyl group, a di(substituted cycloalkyl) aminyl group, adiaryl aminyl group, a di(substituted aryl) aminyl group, a dialkylphosphinyl group, a dicycloalkyl phosphinyl group, a di(substitutedcycloalkyl) phosphinyl group, a diaryl phosphinyl group, adi(substituted aryl) phosphinyl group, an alkyl etheryl group, an aryletheryl group, a substituted aryl etheryl group, an alkyl sulfidylgroup, an aryl sulfidyl group, a substituted aryl sulfidyl group, apyridinyl group, a substituted pyridinyl group, a morphilinyl group, ora substituted morphilinyl group; alternatively, a dialkyl aminyl group,a diaryl aminyl group, a dialkyl phosphinyl group, a diaryl phosphinylgroup, an alkyl etheryl group, an aryl etheryl group, an alkyl sulfidylgroup, an aryl sulfidyl group, a pyridinyl group, or a morphilinylgroup; alternatively, a dialkyl aminyl group, a dicycloalkyl aminylgroup, a di(substituted cycloalkyl) aminyl group, a diaryl aminyl group,a di(substituted aryl) aminyl group, a dialkyl phosphinyl group, adicycloalkyl phosphinyl group, a di(substituted cycloalkyl) phosphinylgroup, a diaryl phosphinyl group, or a di(substituted aryl) phosphinylgroup; alternatively, a dialkyl aminyl group, a diaryl aminyl group, adialkyl phosphinyl group, a diaryl phosphinyl group; or alternatively, adiaryl aminyl group, a di(substituted aryl) aminyl group, or anN-aryl-N-(substituted aryl) aminyl group a diaryl phosphinyl group, adi(substituted aryl) phosphinyl group, or an P-aryl-P-(substituted aryl)phosphinyl group; alternatively, a diaryl aminyl group, a di(substitutedaryl) phosphinyl group, or an N-aryl-N-(substituted aryl) aminyl group adiaryl phosphinyl group, a di(substituted aryl) phosphinyl group, or anP-aryl-P-(substituted aryl) phosphinyl group, an aryl sulfidyl group, asubstituted aryl sulfidyl group, a pyridinyl group, or a substitutedpyridinyl group; or alternatively, a diaryl aminyl group, a diarylphosphinyl group, an aryl sulfidyl group, or a pyridinyl group. In otherembodiments, the metal salt complexing group can be a dialkyl aminylgroup or a dialkyl phosphinyl group; alternatively, a diaryl aminylgroup or a diaryl phosphinyl group; alternatively, a di(substitutedaryl) aminyl group or a di(substituted aryl) phosphinyl group;alternatively, a 2-pyridinyl group or a substituted 2-pyridinyl group;alternatively, an alkyl etheryl group, a phenyl etheryl group, asubstituted aryl etheryl group, an alkyl sulfidyl group, an arylsulfidyl group, or a substituted sulfidyl group; alternatively, an alkyletheryl group or an alkyl sulfidyl group; alternatively, an aryl etherylgroup, a substituted aryl etheryl group, an aryl sulfidyl group, or asubstituted sulfidyl group; alternatively, an aryl etheryl group or asubstituted aryl etheryl group; alternatively, an aryl sulfidyl group,or a substituted aryl sulfidyl group; alternatively, an aryl sulfidylgroup or a substituted aryl sulfidyl group; alternatively, a furanylgroup, a substituted furanyl group, a thienyl group or a substitutedthienyl group; alternatively, a 1-morphilinyl group or a substituted1-morphilinyl group; alternatively, a 2-morphilinyl group or asubstituted 2-morphilinyl group; alternatively, a 2-pyranyl group or asubstituted 2-pyranyl group; alternatively, a 2-tetrahydropyranyl group,a substituted 2-tetrahydropyranyl group; alternatively, a 1-piperidinylgroup, or a substituted 1-piperidinyl group; alternatively, a1-pyrrolidinyl group, a substituted 1-pyrrolidinyl group; alternatively,a 2-pyrrolidinyl group, a substituted 2-pyrrolidinyl group;alternatively, a 2-piperidinyl group, or a substituted 2-piperidinylgroup; alternatively, a 2-quinolinyl group or a substituted 2-quiolinylgroup; alternatively, a 1-pyrrolyl group or a substituted 1-pyrrolylgroup; alternatively, a 2-pyrrolyl group or a substituted 2-pyrrolylgroup; alternatively, a 2-tetrahydrofuranyl group or a substituted2-tetrahydrofuranyl group; or alternatively, a 2-thiophanyl group or asubstituted 2-thiophanyl group. In yet other embodiments, the metal saltcomplexing group can be a diaryl aminyl group; alternatively, adi(substituted aryl) aminyl group; alternatively, a diaryl phosphinylgroup; or alternatively, a di(substituted aryl) phosphinyl group. Alkylgroups, cycloalkyl groups, aryl groups, and aralkyl groups, andsubstituent groups which can be utilized for substituted metalcomplexing groups are independently disclosed herein and can be utilizedwithout limitation to further describe the metal salt complexing group.

In any aspect or embodiment disclosed herein, each alkyl group attachedto the heteroatom of a metal salt complexing group independently can bea C₁ to C₃₀ alkyl group; alternatively, a C₁ to C₂₀ alkyl group;alternatively, a C₁ to C₁₀ alkyl group; or alternatively, a C₁ to C₅alkyl group. In any aspect or embodiment disclosed herein, eachcycloalkyl group attached to the heteroatom of a metal salt complexinggroup independently can be a C₄ to C₃₀ cycloalkyl group; alternatively,a C₄ to C₂₀ cycloalkyl group; alternatively, a C₄ to C₁₅ cycloalkylgroup; or alternatively, a C₄ to C₁₀ cycloalkyl group. In any aspect orembodiment disclosed herein, each substituted cycloalkyl group attachedto the heteroatom of a metal salt complexing group independently can bea C₄ to C₃₀ substituted cycloalkyl group; alternatively, a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₄ to C₁₅ substitutedcycloalkyl group; or alternatively, a C₄ to C₁₀ substituted cycloalkylgroup. In any aspect or embodiment disclosed herein, each aryl groupattached to the heteroatom of a metal salt complexing groupindependently can be a C₆ to C₃₀ aryl group; alternatively, a C₆ to C₂₀aryl group; alternatively, a C₆ to C₁₅ aryl group; or alternatively, aC₆ to C₁₀ aryl group. In any aspect or embodiment disclosed herein, eachsubstituted aryl group attached to the heteroatom of a metal saltcomplexing group independently can be a C₆ to C₃₀ substituted arylgroup; alternatively, a C₆ to C₂₀ substituted aryl group; alternatively,a C₆ to C₁₅ substituted aryl group; or alternatively, a C₆ to C₁₀substituted aryl group. In any aspect or embodiment disclosed herein,each aralkyl group attached to the heteroatom of a metal salt complexinggroup independently can be a C₇ to C₃₀ aralkyl group; alternatively, aC₇ to C₂₀ aralkyl group; alternatively, a C₇ to C₁₅ aralkyl group; oralternatively, a C₇ to C₁₀ aralkyl group. In any aspect or embodimentdisclosed herein, each substituted aryl group attached to the heteroatomof a metal complexing group independently can be a C₇ to C₃₀ substitutedaralkyl group; alternatively, a C₇ to C₂₀ substituted aralkyl group;alternatively, a C₇ to C₁₅ aralkyl group; or alternatively, C₇ to C₁₀substituted aralkyl group. Each substituent of a general cycloalkylgroup, general aryl group, and/or general aralkyl group can be a halogenor a hydrocarboxy group; alternatively, a halogen; or alternatively, ahydrocarboxy group. Substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy groups are independently disclosedherein (e.g. as non-hydrogen substituents of R¹ groups in theN²-phosphinyl amidine compound, among other places). These substituenthalogens, substituent hydrocarbyl groups, and substituent hydrocarboxycan be utilized without limitation to further describe the metal saltcomplexing group.

In an embodiment, the metal salt complexing group (Q¹) of anyN²-phosphinyl amidine compound having a metal salt complexing group (Q¹)can have a metal complexing group structure provided in Table 2.

TABLE 2 Example Metal Salt Complexing Groups, Q¹. —OR^(q1) Structure Q1—SR^(q2) Structure Q2 —NR^(q3)R^(q4) Structure Q3 —PR^(q5)R^(q6)Structure Q4

Structure Q5

Structure Q6

Structure Q7

Structure Q8

Structure Q9

Structure Q10

Structure Q11

Structure Q12

Structure Q13

Structure Q14

Structure Q15

Structure Q16

Structure Q17

Structure Q18

Structure Q19

Structure Q20

Structure Q21

Structure Q22

In some embodiments, the metal salt complexing group can have StructureQ1, Structure Q2, Structure Q3, Structure Q4, Structure Q5, StructureQ6, Structure Q7, Structure Q8, Structure Q9, Structure Q10, StructureQ11, Structure Q12, Structure 13, Structure Q16, Structure Q17,Structure Q18, Structure Q19, or Structure Q20. In other embodiments,the metal salt complexing group can have Structure Q1, Structure Q2,Structure Q3, or Structure Q4; alternatively, Structure Q1 or StructureQ2; alternatively, Structure Q3 or Structure Q4; alternatively,Structure Q5 or Structure Q6; alternatively, Structure Q7 or StructureQ10; alternatively, Structure Q8 or Structure Q9; alternatively,Structure Q11 or Structure Q12; alternatively, Structure Q11 orStructure Q13; alternatively, Structure Q19 or Structure Q20;alternatively, Structure Q1; alternatively, Structure Q2; alternatively,Structure Q3; alternatively, Structure Q4; alternatively, Structure Q5;alternatively, Structure Q6; alternatively, Structure Q7; alternatively,Structure Q8; alternatively, Structure Q9; alternatively, Structure Q10;alternatively, Structure Q11; alternatively, Structure Q12;alternatively, Structure 13; alternatively, Structure Q16;alternatively, Structure Q17; alternatively, Structure Q18;alternatively, Structure Q19; or alternatively, Structure Q20. Infurther embodiments, the metal salt complexing group can have StructureQ14, Structure Q15, Structure Q21, or Structure Q22; alternatively,Structure Q14 or Structure Q15; alternatively, Structure Q21 orStructure Q22; alternatively, Structure Q14; alternatively, StructureQ15; alternatively, Structure Q21; or alternatively, Structure Q22.

In an aspect, R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and R^(q6) withinStructure Q1, Structure Q2, Structure Q3, and/or Structure Q4 can be aC₁ to C₂₀ organyl group consisting essentially of inert functionalgroups; alternatively, a C₁ to C₂₀ organyl group consisting essentiallyof inert functional groups; alternatively, a C₁ to C₁₀ organyl groupconsisting essentially of inert functional groups; or alternatively, aC₁ to C₅ organyl group consisting essentially of inert functionalgroups. In another aspect, R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), andR^(q6) within Structure Q1, Structure Q2, Structure Q3, and/or StructureQ4 can be a C₁ to C₂₀ hydrocarbyl group; alternatively, a C₁ to C₁₅hydrocarbyl group; alternatively, a C₁ to C₁₀ hydrocarbyl group; oralternatively, a C₁ to C₅ hydrocarbyl group.

In an embodiment, R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and R^(q6)within Structure Q1, Structure Q2, Structure Q3, and/or Structure Q4independently can be a C₁ to C₂₀ alkyl group, a C₁ to C₂₀ substitutedalkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substitutedcycloalkyl group, a C₆ to C₂₀ aryl group, a C₆ to C₂₀ substituted arylgroup, a C₇ to C₂₀ aralkyl group, or a C₇ to C₂₀ substituted aralkylgroup; alternatively, a C₁ to C₂₀ alkyl group, a C₄ to C₂₀ cycloalkylgroup, a C₆ to C₂₀ aryl group, or a C₇ to C₂₀ aralkyl group;alternatively, a C₁ to C₂₀ alkyl group or a C₁ to C₂₀ substituted alkylgroup; alternatively, a C₄ to C₂₀ cycloalkyl group or a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₆ to C₂₀ aryl group or aC₆ to C₂₀ substituted aryl group; alternatively, a C₇ to C₂₀ aralkylgroup or a C₇ to C₂₀ substituted aralkyl group; alternatively, a C₁ toC₂₀ alkyl group; alternatively, a C₁ to C₂₀ substituted alkyl group;alternatively, a C₄ to C₂₀ cycloalkyl group; alternatively, a C₄ to C₂₀substituted cycloalkyl group; alternatively, a C₆ to C₂₀ aryl group;alternatively, a C₆ to C₂₀ substituted aryl group; alternatively, a C₇to C₂₀ aralkyl group; or alternatively, a C₇ to C₂₀ substituted aralkylgroup. In some embodiments, R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), andR^(q6) within Structure Q1, Structure Q2, Structure Q3, and/or StructureQ4 independently can be a C₁ to C₁₀ alkyl group, a C₁ to C₁₀ substitutedalkyl group, a C₄ to C₁₅ cycloalkyl group, a C₄ to C₁₅ substitutedcycloalkyl group, a C₆ to C₁₅ aryl group, a C₆ to C₁₅ substituted arylgroup, a C₇ to C₁₅ aralkyl group, or a C₇ to C₁₅ substituted aralkylgroup; alternatively, a C₁ to C₁₀ alkyl group, a C₄ to C₁₅ cycloalkylgroup, a C₆ to C₁₅ aryl group, or a C₇ to C₁₅ aralkyl group;alternatively, a C₁ to C₁₀ alkyl group or a C₁ to C₁₀ substituted alkylgroup; alternatively, a C₄ to C₁₅ cycloalkyl group or a C₄ to C₁₅substituted cycloalkyl group; alternatively, a C₆ to C₁₅ aryl group or aC₆ to C₁₅ substituted aryl group; alternatively, a C₇ to C₁₅aralkylgroup or a C₇ to C₁₅ substituted aralkyl group; alternatively, a C₁ toC₁₀ alkyl group; alternatively, a C₁ to C₁₀ substituted alkyl group;alternatively, a C₄ to C₁₅ cycloalkyl group; alternatively, a C₄ to C₁₅substituted cycloalkyl group; alternatively, a C₆ to C₁₅ aryl group;alternatively, a C₆ to C₁₅ substituted aryl group; alternatively, a C₇to C₁₅ aralkyl group; or alternatively, a C₇ to C₁₅ substituted aralkylgroup. In some embodiments, R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), andR^(q6) within Structure Q1, Structure Q2, Structure Q3, and/or StructureQ4 independently can be a C₁ to C₅ alkyl group, a C₁ to C₅ substitutedalkyl group, a C₄ to C₁₀ cycloalkyl group, a C₄ to C₁₀ substitutedcycloalkyl group, a C₆ to C₁₀ aryl group, a C₆ to C₁₀ substituted arylgroup, a C₇ to C₁₀ aralkyl group, or a C₇ to C₁₀ substituted aralkylgroup; alternatively, a C₁ to C₅ alkyl group, a C₄ to C₁₀ cycloalkylgroup, a C₆ to C₁₀ aryl group, or a C₇ to C₁₀ aralkyl group;alternatively, a C₁ to C₅ alkyl group or a C₁ to C₁₀ substituted alkylgroup; alternatively, a C₄ to C₁₀ cycloalkyl group or a C₄ to C₁₀substituted cycloalkyl group; alternatively, a C₆ to C₁₀ aryl group or aC₆ to C₁₀ substituted aryl group; alternatively, a C₇ to C₁₀ aralkylgroup or a C₇ to C₁₀ substituted aralkyl group; alternatively, a C₁ toC₅ alkyl group; alternatively, a C₁ to C_(s) substituted alkyl group;alternatively, a C₄ to C₁₀ cycloalkyl group; alternatively, a C₄ to C₁₀substituted cycloalkyl group; alternatively, a C₆ to C₁₀ aryl group;alternatively, a C₆ to C₁₀ substituted aryl group; alternatively, a C₇to C₁₀ aralkyl group; or alternatively, a C₇ to C₁₀ substituted aralkylgroup.

In an embodiment, each group attached to the heteroatom of a metal saltcomplexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/orR^(q6) of the metal complexing group having Structures Q1, Q2, Q3,and/or Q4 independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, anoctyl group, a nonyl group, a decyl group, a undecyl group, a dodecylgroup, a tridecyl group, a tetradecyl group, a pentadecyl group, ahexadecyl group, a heptadecyl group, an octadecyl group, or a nonadecylgroup; or alternatively, a methyl group, an ethyl group, a propyl group,a butyl group, a pentyl group, a hexyl group, a heptyl group, an octylgroup, a nonyl group, or a decyl group. In some embodiments, each groupattached to the heteroatom of a metal salt complexing group or R^(q1),R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal saltcomplexing group having Structures Q1, Q2, Q3, and/or Q4 independentlycan be a methyl group, an ethyl group, an n-propyl group, an iso-propylgroup, an n-butyl group, an iso-butyl group, a sec-butyl group, atert-butyl group, an n-pentyl group, an iso-pentyl group, a sec-pentylgroup, or a neopentyl group; alternatively, a methyl group, an ethylgroup, an iso-propyl group, a tert-butyl group, or a neopentyl group;alternatively, a methyl group; alternatively, an ethyl group;alternatively, an n-propyl group; alternatively, an iso-propyl group;alternatively, a tert-butyl group; or alternatively, a neopentyl group.Independently, these alkyl group which can be attached to the heteroatomof the metal complexing group can be a primary alkyl group, a secondaryhydrocarbyl group, or a tertiary alkyl group; alternatively, a primaryalkyl group; alternatively, a secondary alkyl group; or alternatively, atertiary alkyl group. In some embodiments, the alkyl groups which can beutilized as R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6) of themetal salt complexing group having Structures Q1, Q2, Q3, and/or Q4 canbe substituted. Each substituent of a substituted alkyl groupindependently can be a halogen or a hydrocarboxy group; alternatively, ahalogen; or alternatively, a hydrocarboxy group. Substituent halogensand substituent hydrocarboxy groups are independently disclosed herein(e.g. as non-hydrogen substituents of R¹ groups in the N²-phosphinylamidine compound, among other places). These substituent halogens andsubstituent hydrocarboxy groups can be utilized without limitation tofurther describe a substituted alkyl group which can be utilized asR^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6).

In an embodiment, each group attached to the heteroatom of a metal saltcomplexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/orR^(q6) of the metal salt complexing group having Structures Q1, Q2, Q3,and/or Q4 independently can be a cyclobutyl group, a substitutedcyclobutyl group, a cyclopentyl group, a substituted cyclopentyl group,a cyclohexyl group, a substituted cyclohexyl group, a cycloheptyl group,a substituted cycloheptyl group, a cyclooctyl group, or a substitutedcyclooctyl group. In some embodiments, each cycloalkyl group attached tothe heteroatom of a metal salt complexing group can be a cyclopentylgroup, a substituted cyclopentyl group, a cyclohexyl group, or asubstituted cyclohexyl group. In other embodiments, each group attachedto the heteroatom of a metal salt complexing group or R^(q1), R^(q2),R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal complexing grouphaving Structures Q1, Q2, Q3, and/or Q4 independently can be acyclobutyl group or a substituted cyclobutyl group; alternatively, acyclopentyl group or a substituted cyclopentyl group; alternatively, acyclohexyl group or a substituted cyclohexyl group; alternatively, acycloheptyl group or a substituted cycloheptyl group; or alternatively,a cyclooctyl group, or a substituted cyclooctyl group. In furtherembodiments, each group attached to the heteroatom of a metal saltcomplexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/orR^(q6) of the metal salt complexing group having Structures Q1, Q2, Q3,and/or Q4 independently can be a cyclopentyl group; alternatively, asubstituted cyclopentyl group; a cyclohexyl group; or alternatively, asubstituted cyclohexyl group. Each substituent of a cycloalkyl grouphaving a specified number of ring carbon atoms independently can be ahalogen, a hydrocarbyl group, or a hydrocarboxy group; alternatively, ahalogen or a hydrocarbyl group; alternatively, a halogen or ahydrocarboxy group; alternatively, a halogen; alternatively, ahydrocarbyl group; or alternatively, a hydrocarboxy group. Substituenthalogens, substituent hydrocarbyl groups, and substituent hydrocarboxygroups are independently disclosed herein (e.g. as non-hydrogensubstituents of R¹ groups in the N²-phosphinyl amidine compound, amongother places). These substituent halogens, substituent hydrocarbylgroups, and substituent hydrocarboxy can be utilized without limitationto further describe a substituted cycloalkyl group (general or specific)which can be utilized as a group attached to the heteroatom of a metalcomplexing group or utilized R^(q1), R^(q2), R^(q3), R^(q4), R^(q5),and/or R^(q6) of the metal complexing group having Structures Q1, Q2,Q3, and/or Q4.

In other non-limiting embodiments, each group attached to the heteroatomof a metal salt complexing group or R^(q1), R^(q2), R^(q3), R^(q4),R^(q5), and/or R^(q6) of the metal salt complexing group havingStructures Q1, Q2, Q3, and/or Q4 independently can be a cyclohexylgroup, a 2-alkylcyclohexyl group, or a 2,6-dialkylcyclohexyl group;alternatively, cyclopentyl group, a 2-alkylcyclopentyl group, or a2,5-dialkylcyclopentyl group; alternatively, cyclohexyl group;alternatively, a 2-alkylcyclohexyl group; alternatively, a2,6-dialkylcyclohexyl group; alternatively, cyclopentyl group;alternatively, a 2-alkylcyclopentyl group; or alternatively, or2,5-dialkylcyclopentyl group. Alkyl substituent groups are independentlydescribed herein (e.g. as alkyl substituents of R¹ groups in theN²-phosphinyl amidine compound, among other places). These alkylsubstituent groups can be utilized, without limitation, to furtherdescribe an alkylcyclohexyl, dialkylcyclohexyl, alkylcyclopentyl, and/ordialkylcyclopentyl group which can be utilized as a group attached tothe heteroatom of a metal salt complexing group or utilized as R^(q1),R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal saltcomplexing group having Structures Q1, Q2, Q3, and/or Q4. Generally, thealkyl substituents of a disubstituted cyclohexyl or cyclopentyl groupcan be the same; or alternatively, the alkyl substituents of a dialkylcyclohexyl or cyclopentyl group can be different.

In a non-limiting embodiment, each group attached to the heteroatom of ametal salt complexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5),and/or R^(q6) of the metal salt complexing group having Structures Q1,Q2, Q3, and/or Q4 independently can be a 2-methylcyclohexyl group, a2-ethylcyclohexyl group, a 2-isopropylcyclohexyl group, a2-tert-butylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a2,6-diethylcyclohexyl group, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group. In a non-limiting embodiment, eachgroup attached to the heteroatom of a metal salt complexing group orR^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal saltcomplexing group having Structures Q1, Q2, Q3, and/or Q4 independentlycan be, a 2-methylcyclohexyl group, a 2-ethylcyclohexyl group, a2-isopropylcyclohexyl group, or a 2-tert-butylcyclohexyl group;alternatively, a 2,6-dimethylcyclohexyl group, a 2,6-diethylcyclohexylgroup, a 2,6-diisopropylcyclohexyl group, or a2,6-di-tert-butylcyclohexyl group; alternatively, a 2-methylcyclohexylgroup; alternatively, a 2-ethylcyclohexyl group; alternatively, a2-isopropylcyclohexyl group; alternatively, a 2-tert-butylcyclohexylgroup; alternatively, a 2,6-dimethylcyclohexyl group; alternatively, a2,6-diethylcyclohexyl group; alternatively, a 2,6-diisopropylcyclohexylgroup; or alternatively, or 2,6-di-tert-butylcyclohexyl group.

In an embodiment, each group attached to the heteroatom of a metal saltcomplexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/orR^(q6) of the metal complexing salt group having Structures Q1, Q2, Q3,and/or Q4 independently can be a phenyl group, a substituted phenylgroup, a naphthyl group, or a substituted naphthyl group; alternatively,a phenyl group or a substituted phenyl group; alternatively, a naphthylgroup or a substituted naphthyl group; alternatively, a phenyl group ora naphthyl group; alternatively, a phenyl group; alternatively, asubstituted phenyl group; alternatively, a naphthyl group; oralternatively, a substituted naphthyl group. In an embodiment, eachgroup attached to the heteroatom of a metal salt complexing group orR^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal saltcomplexing group having Structures Q1, Q2, Q3 and/or Q4 independentlycan be a 2-substituted phenyl group, a 3-substituted phenyl group, a4-substituted phenyl group, a 2,4-disubstituted phenyl group, a2,6-disubstituted phenyl group, a 3,5-disubstituted phenyl group, or a2,4,6-trisubstituted phenyl group. In other embodiments, each groupattached to the heteroatom of a metal salt complexing group or R^(q1),R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal saltcomplexing group having Structures Q1, Q2, Q3, and/or Q4 independentlycan be a 2-substituted phenyl group, a 4-substituted phenyl group, a2,4-disubstituted phenyl group, or a 2,6-disubstituted phenyl group;alternatively, a 3-substituted phenyl group or a 3,5-disubstitutedphenyl group; alternatively, a 2-substituted phenyl group or a4-substituted phenyl group; alternatively, a 2,4-disubstituted phenylgroup or a 2,6-disubstituted phenyl group; alternatively, a2-substituted phenyl group; alternatively, a 3-substituted phenyl group;alternatively, a 4-substituted phenyl group; alternatively, a2,4-disubstituted phenyl group; alternatively, a 2,6-disubstitutedphenyl group; alternatively, a 3,5-disubstituted phenyl group; oralternatively, a 2,4,6-trisubstituted phenyl group. Each substituent ofa substituted phenyl group (general or specific) or a substitutednaphthyl group (general of specific) independently can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups, and substituent hydrocarboxy groups areindependently disclosed herein (e.g. as non-hydrogen substituents of R¹groups in the N²-phosphinyl amidine compound, among other places). Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy can be utilized without limitation to further describe asubstituted phenyl group (general or specific) or a substituted naphthylgroup (general or specific) which can be utilized as a group attached tothe heteroatom of a metal salt complexing group or R^(q1), R^(q2),R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal salt complexing grouphaving Structures Q1, Q2, Q3, and/or Q4.

In a non-limiting embodiment, each group attached to the heteroatom of ametal salt complexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5),and/or R^(q6) of the metal salt complexing group having Structures Q1,Q2, Q3, and/or Q4 independently can be a phenyl group, a 2-alkylphenylgroup, a 3-alkylphenyl group, a 4-alkylphenyl group, a 2,4-dialkylphenylgroup a 2,6-dialkylphenyl group, a 3,5-dialkylphenyl group, or a2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenyl group, a4-alkylphenyl group, a 2,4-dialkylphenyl group, a 2,6-dialkylphenylgroup, or a 2,4,6-trialkylphenyl group; alternatively, a 2-alkylphenylgroup or a 4-alkylphenyl group; alternatively, a 2,4-dialkylphenyl groupor a 2,6-dialkylphenyl group; alternatively, a 3-alkylphenyl group or a3,5-dialkylphenyl group; alternatively, a 2-alkylphenyl group or a2,6-dialkylphenyl group; alternatively, a 2-alkylphenyl group;alternatively, a 3-alkylphenyl group; alternatively, a 4-alkylphenylgroup; alternatively, a 2,4-dialkylphenyl group; alternatively, a2,6-dialkylphenyl group; alternatively, a 3,5-dialkylphenyl group; oralternatively, a 2,4,6-trialkylphenyl group. Alkyl substituent groupsare independently described herein (e.g. as alkyl substituents of R¹groups in the N²-phosphinyl amidine compound, among other places). Thesealkyl substituent groups can be utilized, without limitation, to furtherdescribe an alkylphenyl, dialkylphenyl, and/or trialkylphenyl groupswhich can be utilized as a group attached to the heteroatom of a metalsalt complexing group or utilized as R^(q1), R^(q2), R^(q3), R^(q4),R^(q5), and/or R^(q6) of the metal salt complexing group havingStructures Q1, Q2, Q3, and/or Q4. Generally, the alkyl substituents ofthe dialkylphenyl groups or trialkyl groups can be the same; oralternatively, the alkyl substituents of a dialkylphenyl group can bedifferent.

In some non-limiting embodiments, each group attached to the heteroatomof a metal salt complexing group or R^(q1), R^(q2), R^(q3), R^(q4),R^(q5), and/or R^(q6) of the metal salt complexing group havingStructures Q1, Q2, Q3, and/or Q4 independently can be a phenyl group, a2-alkoxyphenyl group, a 3-alkoxyphenyl group, a 4-alkoxyphenyl group, or3,5-dialkoxyphenyl group; alternatively, a 2-alkoxyphenyl group or a4-alkoxyphenyl group; alternatively, a 3-alkoxyphenyl group or a3,5-dialkoxyphenyl group; alternatively, a 2-alkoxyphenyl group;alternatively, a 3-alkoxyphenyl group; alternatively, a 4-alkoxyphenylgroup; alternatively, a 3,5-dialkoxyphenyl group. Alkoxy groupsubstituents are independently described herein (e.g. as alkoxysubstituents of R¹ groups in the N²-phosphinyl amidine compound, amongother places). These alkoxy substituents can be utilized, withoutlimitation, to further describe the alkoxyphenyl group(s) and/ordialkoxyphenyl group(s) which can be utilized as a group attached to theheteroatom of a metal salt complexing group or utilized as R^(q1),R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal saltcomplexing group having Structures Q1, Q2, Q3, and/or Q4. Generally, thealkoxy substituents of a dialkoxyphenyl groups can be the same; oralternatively, the alkoxy substituents of a dialkoxyphenyl group can bedifferent.

In other non-limiting embodiments, each group attached to the heteroatomof a metal salt complexing group or R^(q1), R^(q2), R^(q3), R^(q4),R^(q5), and/or R^(q6) of the metal salt complexing group havingStructures Q1, Q2, Q3, and/or Q4 independently can be a phenyl group, a2-halophenyl group, a 3-halophenyl group, a 4-halophenyl group, a2,6-dihalophenyl group, or a 3,5-dialkylphenyl group; alternatively, a2-halophenyl group, a 4-halophenyl group, or a 2,6-dihalophenyl group;alternatively, a 2-halophenyl group or a 4-halophenyl group;alternatively, a 3-halophenyl group or a 3,5-dihalophenyl group;alternatively, a 2-halophenyl group; alternatively, a 3-halophenylgroup; alternatively, a 4-halophenyl group; alternatively, a2,6-dihalophenyl group; or alternatively, a 3,5-dihalophenyl group.Halide substituents are independently described herein (e.g. as halidesubstituents of R¹ groups in the N²-phosphinyl amidine compound, amongother places). These halide substituents can be utilized, withoutlimitation, to further describe a halophenyl group and/or a dihalophenylgroup which can be utilized as a group attached to the heteroatom of ametal complexing group or utilized R^(q1), R^(q2), R^(q3), R^(q4),R^(q5), and/or R^(q6) of the metal complexing group having StructuresQ1, Q2, Q3, and/or Q4. Generally, the halides of a dihalophenyl groupcan be the same; or alternatively, the halides of a dihalophenyl groupcan be different.

In a non-limiting embodiment, each group attached to the heteroatom of ametal salt complexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5),and/or R^(q6) of the metal salt complexing group having Structures Q1,Q2, Q3, and/or Q4 independently can be a phenyl group, a 2-methylphenylgroup, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, a 2-tert-butylphenyl group, a 3-methylphenylgroup, a 2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, a 2-isopropyl-6-methylphenyl group, a3,5-dimethyl group, or a 2,4,6-trimethylphenyl group; alternatively, a2-methylphenyl group, a 2-ethylphenyl group, a 2-n-propylphenyl group, a2-isopropylphenyl group, or a 2-tert-butylphenyl group; alternatively, a2,6-dimethylphenyl group, a 2,6-diethylphenyl group, a2,6-di-n-propylphenyl group, a 2,6-diisopropylphenyl group, a2,6-di-tert-butylphenyl group, or a 2-isopropyl-6-methylphenyl group;alternatively, a 2-methylphenyl group; alternatively, a 2-ethylphenylgroup; alternatively, a 2-n-propylphenyl group; alternatively, a2-isopropylphenyl group; alternatively, a 2-tert-butylphenyl group;alternatively, a 3-methylphenyl group; alternatively, a2,6-dimethylphenyl group; alternatively, a 2,6-diethylphenyl group;alternatively, a 2,6-di-n-propylphenyl group; alternatively, a2,6-diisopropylphenyl group; alternatively, a 2,6-di-tert-butylphenylgroup; alternatively, a 2-isopropyl-6-methylphenyl group; alternatively,a 3,5-dimethylphenyl group; or alternatively, a 2,4,6-trimethylphenylgroup. In some non-limiting embodiments, each group attached to theheteroatom of a metal salt complexing group or R^(q1), R^(q2), R^(q3),R^(q4), R^(q5), and/or R^(q6) of the metal salt complexing group havingStructures Q1, Q2, Q3, and/or Q4 independently can be a phenyl group, a3-methoxyphenyl group, a 3-ethoxyphenyl group, a 3-isopropoxyphenygroup, a 3-tert-butoxyphenyl group, a 4-methoxyphenyl group, a4-ethoxyphenyl group, a 4-isopropoxyphenyl group, a 4-tert-butoxyphenylgroup, a 3,5-dimethoxyphenyl group, a 3,5-diethoxyphenyl group, a3,5-diisopropoxyphenyl group, or a 3,5-di-tert-butoxyphenyl group;alternatively, 3-methoxyphenyl group, a 3-ethoxyphenyl group, a3-isopropoxyphenyl group, or a 3-tert-butoxyphenyl group; alternatively,a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-isopropoxyphenylgroup, or a 4-tert-butoxyphenyl group; or alternatively, a3,5-dimethoxyphenyl group, a 3,5-diethoxyphenyl group, a3,5-diisopropoxyphenyl group, or a 3,5-di-tert-butoxyphenyl group. Inother non-limiting embodiments, each group attached to the heteroatom ofa metal complexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5),and/or R^(q6) of the metal complexing group having Structures Q1, Q2,Q3, and/or Q4 independently can be a 3-methoxyphenyl group;alternatively, a 3-ethoxyphenyl group; alternatively, a3-isopropoxyphenyl group; alternatively, a 3-tert-butoxyphenyl group;alternatively, a 4-methoxyphenyl group; alternatively, a 4-ethoxyphenylgroup; alternatively, a 4-isopropoxyphenyl group; alternatively, a4-tert-butoxyphenyl group; alternatively, a 3,5-dimethoxyphenyl group;alternatively, a 3,5-diethoxyphenyl group; alternatively, a3,5-diisopropoxyphenyl group; or alternatively, a3,5-di-tert-butoxyphenyl group.

In an embodiment, each group attached to the heteroatom of a metal saltcomplexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/orR^(q6) of the metal salt complexing group having Structures Q1, Q2, Q3,and/or Q4 independently can be a benzyl group, a substituted benzylgroup, a 2-phenylethyl group, or a 1-phenylethyl group. In someembodiments, each group attached to the heteroatom of a metal saltcomplexing group or R^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/orR^(q6) of the metal salt complexing group having Structures Q1, Q2, Q3,and/or Q4 independently can be a benzyl group or a substituted benzylgroup; alternatively, a benzyl group; alternatively, a substitutedbenzyl group; alternatively, a 2-phenylethyl group; or alternatively, a1-phenylethyl group. Each substituent of a substituted benzyl group(general or specific) independently can be a halogen, a hydrocarbylgroup, or a hydrocarboxy group; alternatively, a halogen or ahydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups, and substituent hydrocarboxy groups areindependently disclosed herein (e.g. as non-hydrogen substituents of R¹groups in the N²-phosphinyl amidine compound, among other places). Thesesubstituent can be utilized without limitation to further describe asubstituted benzyl group (general or specific) which can be utilized asa group attached to the heteroatom of a metal salt complexing group orR^(q1), R^(q2), R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal saltcomplexing group having Structures Q1, Q2, Q3, and/or Q4.

In an aspect, R^(q21) of the metal salt complexing groups havingStructure Q8, Structure Q9, or Structure Q10 can be a C₁ to C₂₀hydrocarbyl group; alternatively, a C₁ to C₁₅ hydrocarbyl group;alternatively, a C₁ to C₁₀ hydrocarbyl group; or alternatively, a C₁ toC₅ hydrocarbyl group. In some embodiments, R^(q21) of the metal saltcomplexing groups having Structure Q8, Structure Q9, or Structure Q10can be a C₁ to C₂₀ alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₆ toC₂₀ aryl group, or a C₇ to C₂₀ aralkyl group; alternatively, a C₁ to C₂₀alkyl group; alternatively, a C₄ to C₂₀ cycloalkyl group; alternatively,a C₆ to C₂₀ aryl group; or alternatively, a C₇ to C₂₀ aralkyl group. Insome embodiments, R^(q21) of the metal salt complexing groups havingStructure Q8, Structure Q9, or Structure Q10 can be a C₁ to C₁₀ alkylgroup, a C₄ to C₁₅ cycloalkyl group, a C₆ to C₁₅ aryl group, or a C₇ toC₁₅ aralkyl group; alternatively, a C₁ to C₁₀ alkyl group;alternatively, a C₄ to C₁₅ cycloalkyl group; alternatively, a C₆ to C₁₅aryl group; or alternatively, a C₇ to C₁₅ aralkyl group. In otherembodiments, R^(q21) of the metal salt complexing groups havingStructure Q8, Structure Q9, or Structure Q10 can be a C₁ to C₅ alkylgroup, a C₄ to C₁₀ cycloalkyl group, a C₆ to C₁₀ aryl group, or a C₇ toC₁₀ aralkyl group; alternatively, a C₁ to C₅ alkyl group; alternatively,a C₄ to C₁₀ cycloalkyl group; alternatively, a C₆ to C₁₀ aryl group; oralternatively, a C₇ to C₁₀ aralkyl group. General and specific alkylgroups, cycloalkyl groups, aryl group, and aralkyl groups have beendescribed herein as groups which can be utilized as a group attached tothe heteroatom of a metal salt complexing group or as R^(q1), R^(q2),R^(q3), R^(q4), R^(q5), and/or R^(q6) of the metal salt complexing grouphaving Structures Q1, Q2, Q3, and/or Q4. These general and specificalkyl groups, cycloalkyl groups, aryl group, and aralkyl groups can beutilized, without limitation, as R^(q21) of the metal salt complexinggroups having Structure Q8, Structure Q9, or Structure Q10.

In an aspect, each R^(q11), R^(q12), R^(q13), R^(q14), R^(q15), R^(q16),R^(q17), R^(q18), R^(q19), R^(q20), R^(q31), R^(q32), R^(q33), R^(q34),R^(q35), R^(q41), R^(q42), R^(q43), R^(q44), R^(q45), R^(q51), R^(q52),R^(q53), R^(q54), R^(q61), R^(q62), R^(q63), R^(q71), R^(q72), R^(q73),R^(q74), R^(q75), R^(q76), R^(q77), R^(q78), R^(q79), and/or R^(q80) ofStructures Q5-Q22 independently can be a hydrogen or a non-hydrogensubstituent group. Each R^(q11)—R^(q20), R^(q31)—R^(q35),R^(q41)—R^(q45), R^(q51)—R^(q54), R^(q61)—R^(q63), and/orR^(q71)—R^(q80) non-hydrogen, a substituent utilized in the metal saltcomplexing groups having Structures Q5-Q22 can be a halogen, ahydrocarbyl group, or a hydrocarboxy group; alternatively, a halogen ora hydrocarbyl group; alternatively, a halogen or a hydrocarboxy group;alternatively, a halogen; alternatively, a hydrocarbyl group; oralternatively, a hydrocarboxy group. Substituent halogens, substituenthydrocarbyl groups, and substituent hydrocarboxy groups areindependently disclosed herein (e.g. as non-hydrogen substituents R¹ inthe N²-phosphinyl amidine compound, among other places). Thesesubstituent halogens, substituent hydrocarbyl groups, and substituenthydrocarboxy can be utilized without limitation to further describe aR^(q11)—R^(q20), R^(q31)—R^(q35), R^(q41)—R^(q45), R^(q51)—R^(q54),R^(q61)—R^(q63), and/or R^(q71)—R^(q80) non-hydrogen substituentutilized in the metal complexing groups having Structures Q5-Q22.

The linking group (L³) linking the metal salt complexing group to theN²-phosphinyl amidine group or linking the metal salt complexing groupto the N¹ nitrogen atom of the N²-phosphinyl amidine group can be a bondor an organyl group; alternatively, a bond or an organyl groupconsisting of inert functional groups; or alternatively, a bond or ahydrocarbyl group. In other embodiments, the linking group can be abond; alternatively, an organyl group; alternatively, an organyl groupconsisting of inert functional groups; or alternatively, a hydrocarbylgroup. In any aspect or embodiment disclosed herein, the organyl linkinggroup linking the metal salt complexing group to the N²-phosphinylamidine group or linking the metal salt complexing group to the N¹nitrogen atom of the N²-phosphinyl amidine group can be a C₁ to C₁₀organyl group; or alternatively, a C₁ to C₅ organyl group. In any aspector embodiment disclosed herein, the organyl consisting of inertfunctional groups linking the metal salt complexing group to theN²-phosphinyl amidine group or linking the metal salt complexing groupto the N¹ nitrogen atom of the N²-phosphinyl amidine group can be a C₁to C₁₀ organyl group consisting of inert functional groups; oralternatively, a C₁ to C₅ organyl group consisting of inert functionalgroups. In any aspect or embodiment disclosed herein, the hydrocarbyllinking group linking the metal salt complexing group to theN²-phosphinyl amidine group or linking the metal salt complexing groupto the N¹ nitrogen atom of the N²-phosphinyl amidine group can be a C₁to C₁₀ hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarbylgroup.

In some embodiments, the linking group linking the metal salt complexinggroup to the N²-phosphinyl amidine group or linking the metal saltcomplexing group to the N¹ nitrogen atom of the N²-phosphinyl amidinegroup can be —(CR^(1m)R^(1m′))_(m)— where each R^(1m) and R^(1m′)independently can be hydrogen, a methyl group, an ethyl group, ann-propyl group, an isopropyl group, or an n-butyl group and m can be aninteger from 1 to 5. In other embodiments, the linking group can be amethylene group (—CH₂—), an eth-1,2-ylene group (—CH₂CH₂—), aprop-1,3-ylene group (—CH₂CH₂CH₂—), a 1-methyleth-1,2-ylene group(—CH(CH₃)CH₂—), dimethylmethylene group (—C(CH₃)₂—), a but-1,4-ylenegroup (—CH₂CH₂CH₂CH₂—), or a phen-1,2-ylene group. In some non-limitingembodiments, the linking group linking the metal salt complexing groupto the N²-phosphinyl amidine group or linking the metal salt complexinggroup to the N¹ nitrogen atom of the N²-phosphinyl amidine group can bea methylene group (—CH₂—), an eth-1,2-ylene group (—CH₂CH₂—), aprop-1,3-ylene group (—CH₂CH₂CH₂—), or a phen-1,2-ylene group;alternatively, a methylene group (—CH₂—), an eth-1,2-ylene group(—CH₂CH₂—), or a phen-1,2-ylene group; alternatively, an ethylene group(—CH₂CH₂—) or a propylene group (—CH₂CH₂CH₂—); alternatively, aneth-1,2-ylene group (—CH₂CH₂—) or a phen-1,2-ylene group; alternatively,a methylene group (—CH₂—); alternatively, an eth-1,2-ylene group(—CH₂CH₂—); alternatively, a prop-1,3-ylene group (—CH₂CH₂CH₂—); oralternatively, a phen-1,2-ylene group.

In some embodiments, the linking group can have any structure indicatedin Table 3. Within the structures of Table 3, the undesignated valanciesare the points of attachment for the N²-phosphinyl amidine group (or theN¹ nitrogen atom of the N²-phosphinyl amidine group) and the metal saltcomplexing group; each R^(2m) and/or R^(2m′) can independently behydrogen, a methyl group, or an ethyl group; and m can be an integerranging from 1 to 5. In further embodiments, m can be an integer rangingfrom 1 to 3; alternatively, m can be 2 or 3; alternatively, m can be 1;alternatively, m can be 2; or alternatively, m can be 3.

TABLE 3 Example Linking Groups —(CR^(2m)R^(2m′))_(m)— Structure 1QL—(CH₂)_(m)— Structure 2QL —(CH₂)— Structure 3QL —(CH₂CH₂)— Structure 4QL

Structure 5QLIn some embodiments, the linking group can have Structure 1QL, Structure2QL, Structure 3QL, Structure 4QL or Structure 5QL. In some embodiments,the linking group can have Structure 4QL or Structure 5QL. In otherembodiments, the linking group can have Structure 2QL; alternatively,Structure 3QL; alternatively, Structure 4QL; or alternatively, Structure5QL.

Generally, when an N²-phosphinyl amidine compound contains a metal saltcomplexing group and linking group, the metal salt complexing group andlinking group are independent elements of an N²-phosphinyl amidinecompound. Consequently, the N²-phosphinyl amidine compound can bedescribed as having any combination of a metal salt complexing groupdescribed herein and a linking group described herein. In a non-limitingembodiment, when the heteroatom of the metal complexing is not containedin a ring or a ring system, the linking group linking the metal saltcomplexing group to the N²-phosphinyl amidine group or linking the metalsalt complexing group to the N¹ nitrogen atom of the N²-phosphinylamidine group can be a methylene group (—CH₂—), an eth-1,2-ylene group(—CH₂CH₂—), a prop-1,3-ylene group (—CH₂CH₂CH₂—), or a phen-1,2-ylenegroup; alternatively, an ethylene group (—CH₂CH₂—), or a propylene group(—CH₂CH₂CH₂—); alternatively, an eth-1,2-ylene group (—CH₂CH₂—) or aphen-1,2-ylene group; alternatively, a methylene group (—CH₂—);alternatively, an eth-1,2-ylene group (—CH₂CH₂—); alternatively, aprop-1,3-ylene group (—CH₂CH₂CH₂—); or alternatively, a phen-1,2-ylenegroup. In another non-limiting embodiment, when the heteroatom of themetal salt complexing group is contained within a ring, the linkinggroup linking the metal salt complexing group to the N²-phosphinylamidine group or linking the metal salt complexing group to the N¹nitrogen atom of the N²-phosphinyl amidine group can be a bond or amethylene group; alternatively, a bond; or alternatively, a methylenegroup.

In an aspect, this disclosure provides for an N²-phosphinyl amidinemetal salt complex. Generally, the N²-phosphinyl amidine metal saltcomplex can comprise a metal salt complexed to an N²-phosphinyl amidinecompound. In some embodiments, the N²-phosphinyl amidine metal saltcomplex can further comprise a neutral ligand, Q. N²-phosphinyl amidinecompounds are generally described herein and can be utilized, withoutlimitation, to further describe the N²-phosphinyl amidine metal saltcomplex comprising a metal salt complexed to an N²-phosphinyl amidinecompound. In an embodiment, the N²-phosphinyl amidine metal salt complexcan have Structure MC1, MC2, MC3, MC4, MC5, MC6, MC7, MC8, MC9, MC10,MC11, MC13, MC15, MC16, MC18, or MC20; alternatively, Structure MC1,MC2, MC3, MC4, or MC5; alternatively, MC6, MC7, MC8, MC9, or MC10;alternatively, MC11, MC13, or MC15; alternatively, MC16, MC18, or MC20;alternatively, Structure MC1; alternatively, Structure MC2;alternatively, Structure MC3; alternatively, Structure MC4;alternatively, Structure MC5; alternatively, MC6; alternatively, MC7;alternatively, MC8; alternatively, MC9; alternatively, MC10;alternatively, Structure MC11; alternatively, Structure MC13;alternatively, Structure MC15; alternatively, MC16; alternatively, MC18;or alternatively, MC20. In an embodiment, the N²-phosphinyl amidinemetal salt complex comprising only one N²-phosphinyl amidine groupcomplexed to metal salt can be characterized by having the StructureMC1, MC6, MC11, or MC16; alternatively, Structure MC1 or MC6;alternatively, Structure MC11 or MC16; alternatively, Structure MC1 orMC11; or alternatively, Structure MC6 or MC16. In an embodiment, theN²-phosphinyl amidine metal salt complex comprising only twoN²-phosphinyl amidine groups complexed to a metal salt can becharacterized by having Structure MC2, MC3, MC8, MC13, or MC18;alternatively, Structure MC2, MC3, or MC8; alternatively, StructureMC13, or MC18; alternatively, Structure MC2 or MC3; alternatively,Structure MC3 or MC13; or alternatively, Structure MC8 or MC18. In otherembodiments, N²-phosphinyl amidine metal salt complex compounds havingat least one N²-phosphinyl amidine group complexed to a metal salt canbe characterized by having the Structure MC4, MC5, MC9, MC10, MC15, orMC20; alternatively, Structure MC4, MC5, MC9, or MC10; alternatively,Structure MC15, or MC20; alternatively, Structure MC4 or MC5;alternatively, Structure MC9 or MC10; alternatively, Structure MC5 orMC15; or alternatively, Structure MC10 or MC20.

R¹, R², R³, R⁴, R⁵, D¹, D², L¹, L², L³, Q¹, q, r, M, X, Q, p, and awithin the N2-phosphinyl amidine metal salt complex Structures MC1-MC10,MC11, MC13, MC15, MC16, MC18, and/or MC20 are independently describedherein and these description can be utilized in any combination tofurther describe the N²-phosphinyl amidine metal salt complexes of thisdisclosure. Generally, MX_(p) or MX_(p)Q_(a) represents the metal saltof the metal complex, Q represents a neutral ligand, and a representsthe number of neutral ligands in the N²-phosphinyl amidine metal saltcomplex. The N²-phosphinyl amidine compound features R¹, R², R³, R⁴, R⁵,D¹, D², L¹, L², L³, Q¹, q, and r are described for N²-phosphinyl amidinecompounds having Structures Structures NP1-NP10, NP11, NP13, NP15, NP16,NP18, and/or NP20 can be utilized without limitation to describe theN²-phosphinyl amidine metal salt complexes having Structures StructuresMC1-MC10, MC11, MC13, MC15, MC16, MC18, and/or MC20.

Generally, the metal salt, MX_(p) or MX_(p)Q_(a), of the N²-phosphinylamidine metal salt complex comprising a metal salt complexed to anN²-phosphinyl amidine compound can comprise a cationic metal, M, and amonoanionic ligand, X. In some embodiments, the metal salt can furthercomprises a neutral ligand which may or may not be present in theN²-phosphinyl amidine metal salt complex comprising a metal saltcomplexed to an N²-phosphinyl amidine compound.

Generally, the metal atom of the metal salt, MX_(p) or MX_(p)Q_(a) canbe any metal atom. In an aspect, the metal atom of the metal salt can bea transition metal. In an embodiment, suitable metal salts can comprise,or consist essentially of, a Group 3-12 transition metal; alternatively,a Group 4-10 transition metal; alternatively, a Group 6-9 transitionmetal; alternatively, a Group 7-8 transition metal; alternatively, aGroup 4 transition metal; alternatively, a Group 5 transition metalalternatively, a Group 6 transition metal; alternatively, a Group 7transition metal; alternatively, a Group 8 transition metal;alternatively, a Group 9 transition metal; or alternatively, a Group 10transition metal. In some embodiments, the metal salt can comprisetitanium, zirconium, hafnium, vanadium, niobium, tantalum, chromium,molybdenum, tungsten, manganese, iron, cobalt, nickel, palladium,platinum, copper, or zinc. In other embodiments, the metal salt cancomprise titanium, zirconium, vanadium, chromium, molybdenum, tungsten,iron, cobalt, nickel, palladium, or platinum; alternatively, chromium,iron, cobalt, or nickel; alternatively, titanium, zirconium or hafnium;alternatively, vanadium or niobium; alternatively, chromium, molybdenumor tungsten; alternatively, iron or cobalt; or alternatively, nickel,palladium, platinum, copper, or zinc. In other embodiments, the metalsalt can comprise titanium; alternatively, zirconium; alternatively,hafnium; alternatively, vanadium; alternatively, niobium; alternatively,tantalum; alternatively, chromium; alternatively, molybdenum;alternatively, tungsten; alternatively, manganese; alternatively, iron;alternatively, cobalt; alternatively, nickel; alternatively, palladium;alternatively, platinum; alternatively, copper; or alternatively, zinc.

Generally, the metal atom of the transition metal salt, MX_(p) orMX_(p)Q_(a) can have any positive oxidation state available to the metalatom. In an embodiment, the transition metal can have an oxidation stateof from +2 to +6; alternatively, from +2 to +4; or alternatively, from+2 to +3. In some embodiments, the metal atom of the transition metalsalt, MX_(p) or MX_(p)Q_(a) can have an oxidation state or +1;alternatively, +2; alternatively, +3; or alternatively, +4.

The anion X, of the transition metal salt can be any monoanion. In anembodiment, the monoanion, X, can be a halide, a carboxylate, aβ-diketonate, a hydrcarboxide, a nitrate, or a chlorate. In someembodiments, the monoanion, X, can be a halide, a carboxylate, aβ-diketonate, or a hydrocarboxide. In any aspect or embodiment, thehydrocarboxide can be an aloxide, an aryloxide, or an aralkoxide.Generally, hydrocarboxide (and subdivisions of hydrocarboxide) are theanion analogues of the hydrocarboxy group. In other embodiments, themonoanion, X, can be a halide, a carboxylate, a β-diketonate, or analkoxide; or alternatively, a halide or a β-diketonate. In otherembodiments, the monoanion X can be a halide; alternatively, acarboxylate; alternatively, a β-diketonate; alternatively, ahydrocarboxide; alternatively, an alkoxide; or alternatively, anaryloxide. Generally, the number, p, of monoanions, X, can equal theoxidation state of the metal atom. In an embodiment, the number, p, ofmonoanions, X, can be from 2 to 6; alternatively, from 2 to 4;alternatively, from 2 to 3; alternatively, 1; alternatively, 2;alternatively, 3; or alternatively, 4.

Generally, each halide monoanion independently can be fluorine,chlorine, bromine, or iodine; or alternatively, chlorine, bromine, oriodine. In an embodiment, each halide monoanion can be chlorine;alternatively, bromine; or alternatively, iodine.

Generally, the carboxylate, a β-diketonate, hydrocarboxide (alsoalkoxide, aryloxide, or aralkoxide) can be any C₁ to C₂₀ carboxylate, aβ-diketonate, hydrocarboxide (also alkoxide, aryloxide or aralkoxide);or alternatively, any C₁ to C₁₀ carboxylate, a β-diketonate,hydrocarboxide (also alkoxide, aryloxide, or aralkoxide). In someembodiments, the anion, X, can be a C₁ to C₂₀ carboxylate;alternatively, a C₁ to C₂₀ carboxylate; alternatively, a C₁ to C₂₀β-diketonate; alternatively, a C₁ to C₁₀ β-diketonate; alternatively, aC₁ to C₂₀ hydrocarboxide; alternatively, a C₁ to C₁₀ hydrocarboxide;alternatively, a C₁ to C₂₀ alkoxide; alternatively, a C₁ to C₁₀alkoxide; alternatively, a C₆ to C₂₀ aryloxide; or alternatively, a C₆to C₁₀ aryloxide.

In an aspect, each carboxylate monoanion independently can be acetate, apropionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, anoctanoate, a nonanoate, a decanoate, an undecanoate, a dodecanoate, atridecanoate, a tetradecanoate, a pentadecanoate, a hexadecanoate, aheptadecanoate, or an octadecanoate; or alternatively, a pentanoate, ahexanoate, a heptanoate, a octanoate, a nonanoate, a decanoate, aundecanoate, or a dodecanoate. In an embodiment, each carboxylatemonoanion independently can be acetate, propionate, n-butyrate, valerate(n-pentanoate), neo-pentanoate, capronate (n-hexanoate), n-heptanoate,caprylate (n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate(n-decanoate), n-undecanoate, laurate (n-dodecanoate), or stearate(n-octadecanoate); alternatively, valerate (n-pentanoate),neo-pentanoate, capronate (n-hexanoate), n-heptanoate, caprylate(n-octanoate), 2-ethylhexanoate, n-nonanoate, caprate (n-decanoate),n-undecanoate, or laurate (n-dodecanoate); alternatively, capronate(n-hexanoate); alternatively, n-heptanoate; alternatively, caprylate(n-octanoate); or alternatively, 2-ethylhexanoate. In some embodiments,the carboxylate anion can be triflate (trifluoroacetate).

In an aspect, each β-diketonate independently can be acetylacetonate(alternatively, 2,4-pentanedionate), hexafluoroacetylacetone(alternatively, 1,1,1,5,5,5-hexafluoro-2,4-pentanediuonate, orbenzoylacetonate); alternatively, acetylacetonate; alternatively,hexafluoroacetylacetone; or alternatively, benzoylacetonate. In anaspect, each alkoxide monoanion independently can be methoxide,ethoxide, a propoxide, or a butoxide. In an embodiment, each alkoxidemonoanion independently can be methoxide, ethoxide, isopropoxide, ortert-butoxide; alternatively, methoxide; alternatively, an ethoxide;alternatively, an iso-propoxide; or alternatively, a tert-butoxide. Inan aspect, the aryloxide can be phenoxide.

Generally, neutral ligand of the transition metal salt or theN²-phosphinyl amidine metal salt complex comprising a transition metalsalt complexed to an N²-phosphinyl amidine compound, if present,independently can be any neutral ligand that forms an isolatablecompound of the metal salt or N²-phosphinyl amidine metal salt complexcomprising a transition metal salt complexed to an N²-phosphinyl amidinecompound. In an aspect, each neutral ligand independently can be anitrile or an ether. In an embodiment, the neutral ligand can be anitrile; or alternatively, an ether. The number of neutral ligands, a,of the metal salt or N²-phosphinyl amidine metal salt complex comprisingtransition metal salt complexed to an N²-phosphinyl amidine compound canbe any number that forms an isolatable metal salt or N²-phosphinylamidine metal salt complex comprising a transition metal salt complexedto an N²-phosphinyl amidine compound. In an aspect, the number ofneutral ligands can be from 0 to 6; alternatively, 0 to 3;alternatively, 0; alternatively, 1; alternatively, 2; alternatively, 3;or alternatively, 4. It should be noted that the neutral ligand of theN²-phosphinyl amidine metal salt complex comprising a transition metalsalt complexed to an N²-phosphinyl amidine compound does not have to bethe same, if present, as the neutral ligand of the transition metal saltused to form the N²-phosphinyl amidine metal salt complex. Additionally,a metal salt not having a neutral ligan can be utilized to prepare anN²-phosphinyl amidine metal salt complex comprising a transition metalsalt complexed to an N²-phosphinyl amidine compound having a neutralligand.

Generally, each neutral nitrile ligand independently can be a C₂ to C₂₀nitrile; or alternatively, a C₂ to C₁₀ nitrile. In an embodiment, eachneutral nitrile ligand independently can be a C₂-C₂₀ aliphatic nitrile,a C₇-C₂₀ aromatic nitrile, a C₈-C₂₀ aralkane nitrile, or any combinationthereof; alternatively, a C₂-C₂₀ aliphatic nitrile; alternatively, aC₇-C₂₀ aromatic nitrile; or alternatively, a C₈-C₂₀ aralkane nitrile. Insome embodiments, each neutral nitrile ligand independently can be aC₂-C₁₀ aliphatic nitrile, a C₇-C₁₀ aromatic nitrile, a C₈-C₁₀ aralkanenitrile, or any combination thereof; alternatively, a C₁-C₁₀ aliphaticnitrile; alternatively, a C₇-C₁₀ aromatic nitrile; or alternatively, aC₈-C₁₀ aralkane nitrile.

In an embodiment, each aliphatic nitrile independently can beacetonitrile, propionitrile, a butyronitrile, or any combinationthereof; alternatively, acetonitrile; alternatively, propionitrile;alternatively, or a butyronitrile. In an embodiment, each aromaticnitrile independently can be benzonitrile, 2-methylbenzonitrile,3-methylbenzonitrile, 4-methylbenzonitrile, 2-ethylbenzonitrile,3-ethylbenzonitrile, 4-ethylbenzonitrile, or any combination thereof;alternatively, benzonitrile; alternatively, 2-methylbenzonitrile;alternatively, 3-methylbenzonitrile; alternatively,4-methylbenzonitrile; alternatively, 2-ethylbenzonitrile; alternatively,3-ethylbenzonitrile; or alternatively, 4-ethylbenzonitrile.

Generally, each neutral ether ligand independently can be a C₂ to C₄₀ether; alternatively, a C₂ to C₃₀ ether; or alternatively, a C₂ to C₂₀ether. In an embodiment, neutral ligand indendently can be a C₂ to C₄₀aliphatic acyclic ether, a C₃ to C₄₀ aliphatic cyclic ether, a C₄ to C₄₀aromatic cyclic ether, or a C₁₂ to C₄₀ diaryl ether; alternatively, a C₂to C₄₀ aliphatic acyclic ether; alternatively, a C₃ to C₄₀ aliphaticcyclic ether; alternatively, a C₄ to C₄₀ aromatic cyclic ether; oralternatively, a C₁₂ to C₄₀ diaryl ether. In some embodiments, eachneutral ligand independently can be a C₂ to C₃₀ aliphatic acyclic ether,a C₃ to C₃₀ aliphatic cyclic ether, a C₄ to C₃₀ aromatic cyclic ether,or a C₁₂ to C₃₀ diaryl ether; alternatively, a C₂ to C₃₀ aliphaticacyclic ether; alternatively, a C₃ to C₃₀ aliphatic cyclic ether;alternatively, a C₄ to C₃₀ aromatic cyclic ether; or alternatively, aC₁₂ to C₃₀ diaryl ether. In other embodiments, each neutral ligandindependently can be a C₂ to C₂₀ aliphatic acyclic ether, a C₃ to C₂₀aliphatic cyclic ether, a C₄ to C₂₀ aromatic cyclic ether, or a C₁₂ toC₂₀ diaryl ether; alternatively, a C₂ to C₂₀ aliphatic acyclic ether;alternatively, a C₃ to C₂₀ aliphatic cyclic ether; alternatively, a C₄to C₂₀ aromatic cyclic ether; or alternatively, a C₁₂ to C₂₀ diarylether.

In an embodiment, the aliphatic acyclic ether can be dimethyl ether,diethyl ether, a dipropyl ether, a dibutyl ether, methyl ethyl ether, amethyl propyl ether, a methyl butyl ether, or any combination thereof.In some embodiments, the aliphatic acyclic ether can be dimethyl ether;alternatively, diethyl ether; alternatively, a dipropyl ether;alternatively, a dibutyl ether; alternatively, methyl ethyl ether;alternatively, a methyl propyl ether; or alternatively, a methyl butylether.

In an embodiment, the aliphatic cyclic ether can be tetrahydrofuran, asubstituted tetrahydrofuran, a dihydrofuran, a substituted dihydrofuran,1,3-dioxolane, a substituted 1,3-dioxolane, tetrahydropyran, asubstituted tetrahydropyran, a dihydropyran, a substituted dihydropyran,pyran, a substituted pyran, a dioxane, or a substituted dioxane;alternatively, tetrahydrofuran or a substituted tetrahydrofuran;alternatively, a dihydrofuran or a substituted dihydrofuran;alternatively, 1,3-dioxolane or a substituted 1,3-dioxolane;alternatively, tetrahydropyran or a substituted tetrahydropyran;alternatively, a dihydropyran or a substituted dihydropyran;alternatively, pyran or a substituted pyran; or alternatively, a dioxaneor a substituted dioxane. In some embodiments, the aliphatic cyclicether can be tetrahydrofuran, tetrahydropyran, or dioxane, or anycombination thereof; alternatively, tetrahydrofuran; alternatively,tetrahydropyran; or alternatively, dioxane.

In an embodiment, the aromatic cyclic ether can be furan, a substitutedfuran, benzofuran, a substituted benzofuran, isobenzofuran, asubstituted isobenzofuran, dibenzofuran, a substituted dibenzofuran, orany combination thereof; alternatively, furan or a substituted furan;alternatively, benzofuran or a substituted benzofuran; alternatively,isobenzofuran or a substituted isobenzofuran; or alternatively, adibenzofuran or a substituted dibenzofuran. In some embodiments, thearomatic cyclic ether can be furan, benzofuran, isobenzofuran,dibenzofuran, or any combination thereof; alternatively, furan;alternatively, benzofuran; alternatively, isobenzofuran; oralternatively, dibenzofuran.

In an embodiment, the diaryl ether can be diphenyl ether, a substituteddiphenyl ether, ditolyl ether, a substituted ditolyl ether, or anycombination thereof; alternatively, diphenyl ether or a substituteddiphenyl ether; or alternatively, ditolyl ether or a substituted ditolylether. In some embodiments, the diaryl ether can be diphenyl ether orditolyl ether; alternatively, diphenyl ether; or ditolyl ether.

Generally, each substituent of any subtituted neutral ligand, Q,described herein independently can be a halide and a C₁ to C₁₀hydrocarbyl group; alternatively, a halide and a C₁ to C₆ hydrocarbylgroup; alternatively, a halide; alternatively, a C₁ to C₁₀ hydrocarbylgroup; or alternatively, a C₁ to C₆ hydrocarbyl group. In an embodiment,each substituent of any subtituted neutral ligand, Q, described hereinindependently can be a halide and a C₁ to C₁₀ alkyl group;alternatively, a halide and a C₁ to C₆ alkyl; alternatively, a halide;alternatively, a C₁ to C₁₀ alkyl group; or alternatively, a C₁ to C₆alkyl group. Generally, each halide substituent independently can beindependently a fluoride, chloride, bromide, or iodide; alternatively,fluoride; alternatively, chloride; alternatively, bromide; oralternatively, iodide. Generally, each hydrocarbyl substituentindependently can be a methyl group, an ethyl group a propyl group, abutyl group, a pentyl group, a cyclopentyl group, a hexyl group, acyclohexyl group, or a phenyl group; alternatively, a cyclopentyl group;a cyclohexyl group; or alternatively, a phenyl group. Generally, eachalkyl substituents independently can be a methyl group, an ethyl group apropyl group, a butyl group, or pentyl group; alternatively, a methylgroup, an ethyl group, an iso-propyl group, a tert-butyl group, or aneo-pentyl group; alternatively, a methyl group; alternatively, an ethylgroup; alternatively, an iso-propyl group; alternatively, a tert-butylgroup; or alternatively, a neo-pentyl group.

The features of the transition metal salts have been independentlydescribed herein and may be utilized in any combination to describe thetransition metal salt of the N²-phosphinyl amidine metal salt complexcomprising a transition metal salt complexed to an N²-phosphinyl amidinecompound.

In a non-limiting embodiment, the transition metal salts which can beutilized include chromium(II) halides, chromium(III) halides,chromium(II) carboxylates, chromium(III) carboxylates, chromium(II)β-diketonates, chromium(III) β-diketonates, chromium(II) halide (THF)complexes, chromium(III) halide (THF) complexes, iron(II) halides,iron(III) halides, iron(II) carboxylates, iron(III) carboxylates,iron(II) β-diketonates, iron(III) β-diketonates, cobalt(II) halides,cobalt(III) halides, cobalt(II) carboxylates, cobalt(III) carboxylates,cobalt(II) β-diketonates, cobalt(III) β-diketonates, nickel(II) halides,nickel(II) carboxylates, nickel(II) β-diketonates, palladium(II)halides, palladium(II) carboxylates, palladium(II) β-diketonates,platinum(II) halides, platinum(IV) halides, platinum(II) carboxylates,or platinum(IV) carboxylates. In some non-limiting embodiments, thetransition metal salt can be a chromium(II) halide, a chromium(III)halide, a chromium (II) carboxylate, a chromium(III) carboxylate, achromium(II) β-diketonate, a chromium(III) β-diketonate, a chromium(II)halide (THF) complex, or a chromium(III) halide (THF) complex;alternatively, an iron(II) halide, an iron(III) halide, an iron(II)carboxylate, an iron(III) carboxylate, an iron(II) β-diketonate, or aniron(III) β-diketonate; alternatively, a cobalt(II) halide, acobalt(III) halide, a cobalt(II) carboxylate, a cobalt(III) carboxylate,a cobalt(II) β-diketonate, or a cobalt(III) β-diketonate; alternatively,a nickel(II) halide, a nickel(II) carboxylate, or a nickel(II)β-diketonate; alternatively, a palladium(II) halide, a palladium(II)carboxylate, or a palladium(II) β-diketonate; or alternatively, aplatinum(II) halide, a platinum(IV) halide, a platinum(II) carboxylate,or a platinum(IV) carboxylate. In some embodiments, the transition metalsalt can be a chromium(III) halide, a chromium(III) carboxylate, achromium(III) β-diketonate, a chromium(III) halide (THF) complex;alternatively, an iron(III) halide, an iron(III) carboxylate, or aniron(III) β-diketonate; or alternatively, a cobalt(III) halide, acobalt(III) carboxylate, or a cobalt(III) β-diketonate. In otherembodiments, the transition metal salt can be a be a chromium(II)halide; alternatively, a chromium(III) halide; alternatively, a chromium(II) carboxylate; alternatively, a chromium(III) carboxylate;alternatively, a chromium(II) β-diketonate; alternatively, achromium(III) β-diketonate; alternatively, a chromium(II) halide (THF)complex; alternatively, a chromium(III) halide (THF) complex;alternatively, an iron(II) halide; alternatively, an iron(III) halide;alternatively, an iron(II) carboxylate; alternatively, an iron(III)carboxylate; alternatively, an iron(II) β-diketonate; alternatively, aniron(III) β-diketonate; alternatively, a cobalt(II) halide;alternatively, a cobalt(III) halide; alternatively, a cobalt(II)carboxylate; alternatively, a cobalt(III) carboxylate; alternatively, acobalt(II) β-diketonate; alternatively, a cobalt(III) β-diketonate;alternatively, a nickel(II) halide; alternatively, a nickel(II)carboxylate; alternatively, a nickel(II) β-diketonate; alternatively, apalladium(II) halide; alternatively, a palladium(II) carboxylate;alternatively, a palladium(II) β-diketonate; alternatively, aplatinum(II) halide; alternatively, a platinum(IV) halide;alternatively, a platinum(II) carboxylate; or alternatively, aplatinum(IV) carboxylate.

In some non-limiting embodiments, transition metal salts which can beutilized include chromium(II) chloride, chromium(III) chloride,chromium(II) fluoride, chromium(III) fluoride, chromium(II) bromide,chromium(III) bromide, chromium(II) iodide, chromium(III) iodide,chromium(III) chloride (THF) complex, chromium(II) acetate,chromium(III) acetate, chromium(II) 2-ethylhexanoate, chromium(III)2-ethylhexanoate, chromium(II) triflate, chromium(III) triflate,chromium(III) nitrate, chromium(III) acetylacetonate, chromium(III)hexafluoracetylacetonate, chromium(III) benzoylacetonate, iron(II)chloride, iron(III) chloride, iron(II) fluoride, iron(III) fluoride,iron(II) bromide, iron(III) bromide, iron(II) iodide, iron(III) iodide,iron(II) acetate, iron(III) acetate, iron(II) acetylacetonate, iron(III)acetylacetonate, iron(II) 2-ethylhexanoate, iron(III) 2-ethylhexanoate,iron(II) triflate, iron(III) triflate, iron(III) nitrate, cobalt(II)chloride, cobalt(III) chloride, cobalt(II) fluoride, cobalt(III)fluoride, cobalt(II) bromide, cobalt(III) bromide, cobalt(II) iodide,cobalt(III) iodide, cobalt(II) acetate, cobalt(III) acetate, cobalt(II)acetylacetonate, cobalt(III) acetylacetonate, cobalt(II)2-ethylhexanoate, cobalt(III) 2-ethylhexanoate, cobalt(II) triflate,cobalt(III) triflate, cobalt(III) nitrate, nickel(II) chloride,nickel(II) fluoride, nickel(II) bromide, nickel(II) iodide, nickel(II)acetate, nickel(II) 2-ethylhexanoate, nickel(II) triflate, nickel(II)nitrate, nickel(II) acetylacetonate, nickel(II) benzoylacetonate,nickel(II) hexafluoracetylacetonate, palladium(II) chloride,palladium(II) fluoride, palladium(II) bromide, palladium(II) iodide,palladium(II) acetate, palladium(II) acetylacetonate, palladium(II)nitrate, platinum(II) chloride, platinum(II) bromide, platinum(II)iodide, or platinum(IV) chloride. In other embodiments, the transitionmetal salt can be chromium(II) chloride, chromium(III) chloride,chromium(II) fluoride, chromium(III) fluoride, chromium(II) bromide,chromium(III) bromide, chromium(II) iodide, chromium(III) iodide,chromium(III) chloride (THF) complex, chromium(II) acetate,chromium(III) acetate, chromium(II) 2-ethylhexanoate, chromium(III)2-ethylhexanoate chromium(II) triflate, chromium(III) triflate,chromium(III) nitrate, chromium(III) acetylacetonate, chromium(III)hexafluoracetylacetonate, or chromium(III) benzoylacetonate;alternatively, iron(II) chloride, iron(III) chloride, iron(II) fluoride,iron(III) fluoride, iron(II) bromide, iron(III) bromide, iron(II)iodide, iron(III) iodide, iron(II) acetate, iron(III) acetate, iron(II)acetylacetonate, iron(III) acetylacetonate, iron(II) 2-ethylhexanoate,iron(III) 2-ethylhexanoate, iron(II) triflate, iron(III) triflate, oriron(III) nitrate; alternatively, cobalt(II) chloride, cobalt(III)chloride, cobalt(II) fluoride, cobalt(III) fluoride, cobalt(II) bromide,cobalt(III) bromide, cobalt(II) iodide, cobalt(III) iodide, cobalt(II)acetate, cobalt(III) acetate, cobalt(II) acetylacetonate, cobalt(III)acetylacetonate, cobalt(II) 2-ethylhexanoate, cobalt(III)2-ethylhexanoate, cobalt(II) triflate, cobalt(III) triflate, orcobalt(III) nitrate; alternatively, nickel(II) chloride, nickel(II)fluoride, nickel(II) bromide, nickel(II) iodide, nickel(II) acetate,nickel(II) 2-ethylhexanoate, nickel(II) triflate, nickel(II) nitrate,nickel(II) acetylacetonate, nickel(II) benzoylacetonate, or nickel(II)hexafluoracetylacetonate; alternatively, palladium(II) chloride,palladium(II) fluoride, palladium(II) bromide, palladium(II) iodide,palladium(II) acetate, palladium(II) acetylacetonate, or palladium(II)nitrate; or alternatively, platinum(II) chloride, platinum(II) bromide,platinum(II) iodide, or platinum(IV) chloride. In yet other embodiments,the transition metal salt can be chromium(III) chloride, chromium(III)fluoride, chromium(III) bromide, chromium(III) iodide, chromium(III)chloride (THF) complex, chromium(III) acetate, chromium(III)2-ethylhexanoate, chromium(III) triflate, chromium(III) nitrate,chromium(III) acetylacetonate, chromium(III) hexafluoracetylacetonate,or chromium(III) benzoylacetonate; or alternatively, iron(III) chloride,iron(III) fluoride, iron(III) bromide, iron(III) iodide, iron(III)acetate, iron(III) acetylacetonate, iron(III) 2-ethylhexanoate,iron(III) triflate, or iron(III) nitrate. In further embodiments, thetransition metal salt can be chromium(III) chloride, chromium(III)chloride (THF) complex, or chromium(III) acetylacetonate; oralternatively, iron(III) chloride, or iron(III) acetylacetonate.

In some non-limiting embodiments, transition metal salts which can beutilized include chromium(II) chloride; alternatively, chromium(III)chloride; alternatively, chromium(II) fluoride; alternatively,chromium(III) fluoride; alternatively, chromium(II) bromide;alternatively, chromium(III) bromide; alternatively, chromium(II)iodide; alternatively, chromium(III) iodide; alternatively,chromium(III) chloride (THF) complex; alternatively, chromium(II)acetate; alternatively, chromium(III) acetate; alternatively,chromium(II) 2-ethylhexanoate; alternatively, chromium(III)2-ethylhexanoate; alternatively, chromium(II) triflate; alternatively,chromium(III) triflate; alternatively, chromium(III) nitrate;alternatively, chromium(III) acetylacetonate; alternatively,chromium(III) hexafluoracetylacetonate; alternatively, chromium(III)benzoylacetonate; alternatively, iron(II) chloride; alternatively,iron(III) chloride; alternatively, iron(II) fluoride; alternatively,iron(III) fluoride; alternatively, iron(II) bromide; alternatively,iron(III) bromide; alternatively, iron(II) iodide; alternatively,iron(III) iodide; alternatively, iron(II) acetate; alternatively,iron(III) acetate; alternatively, iron(II) acetylacetonate;alternatively, iron(III) acetylacetonate; alternatively, iron(II)2-ethylhexanoate; alternatively, iron(III) 2-ethylhexanoate;alternatively, iron(II) triflate; alternatively, iron(III) triflate;alternatively, iron(III) nitrate; alternatively, cobalt(II) chloride;alternatively, cobalt(III) chloride; alternatively, cobalt(II) fluoride;alternatively, cobalt(III) fluoride; alternatively, cobalt(II) bromide;alternatively, cobalt(III) bromide; alternatively, cobalt(II) iodide;alternatively, cobalt(III) iodide; alternatively, cobalt(II) acetate;alternatively, cobalt(III) acetate; alternatively, cobalt(II)acetylacetonate; alternatively, cobalt(III) acetylacetonate;alternatively, cobalt(II) 2-ethylhexanoate; alternatively, cobalt(III)2-ethylhexanoate; alternatively, cobalt(II) triflate; alternatively,cobalt(III) triflate; alternatively, cobalt(III) nitrate; alternatively,nickel(II) chloride; alternatively, nickel(II) fluoride; alternatively,nickel(II) bromide; alternatively, nickel(II) iodide; alternatively,nickel(II) acetate; alternatively, nickel(II) 2-ethylhexanoate;alternatively, nickel(II) triflate; alternatively, nickel(II) nitrate;alternatively, nickel(II) acetylacetonate; alternatively, nickel(II)benzoylacetonate; alternatively, nickel(II) hexafluoracetylacetonate;alternatively, palladium(II) chloride; alternatively, palladium(II)fluoride; alternatively, palladium(II) bromide; alternatively,palladium(II) iodide; alternatively, palladium(II) acetate;alternatively, palladium(II) acetylacetonate; alternatively,palladium(II) nitrate; alternatively, platinum(II) chloride;alternatively, platinum(II) bromide; alternatively, platinum(II) iodide;or alternatively, platinum(IV) chloride.

It should be appreciated, that a given N²-phosphinyl amidine metal saltcomplex can have one or more neutral ligands even when the metal saltutilized to produce the N²-phosphinyl amidine metal salt complex did nothave any neutral ligands.

In an aspect, the present disclosure relates to catalyst systemscomprising an N²-phosphinyl amidine compound and a metal salt;alternatively, an N²-phosphinyl amidine metal salt complex. In anembodiment, the catalyst system can comprise, or consist essentially of,an N²-phosphinyl amidine metal salt complex and a metal alkyl; oralternatively, an N²-phosphinyl amidine metal salt complex and analuminoxane. In another aspect, the catalyst system can comprise, orconsist essentially of, an N²-phosphinyl amidine compound, a metal salt,and a metal alkyl; or alternatively, an N²-phosphinyl amidine compound,a metal salt, and an aluminoxane. The N²-phosphinyl amidine metal saltcomplex, metal salt, N²-phosphinyl amidine compound, metal alky, andaluminoxane which can be utilized in various aspects and/or embodimentsof the catalyst system are independently described herein and can beutilized in any combination and without limitation to describe variouscatalyst systems of this disclosure.

The N²-phosphinyl amidine metal salt complex(es) and metal alkyls whichcan be utilized in various catalyst systems of this disclosure cancomprise a metal salt complexed to an N²-phosphinyl amidine compound.The N²-phosphinyl amidine metal salt complexes, metal salts, andN²-phosphinyl amidine compounds are independently described herein andcan be utilized without limitation to describe an N²-phosphinyl amidinemetal salt complex which can be utilized in various catalyst systems ofthis disclosure.

Generally, the metal alkyl compound which can be utilized in thecatalyst system of this disclosure can be any heteroleptic or homolepticmetal alkyl compound. In an embodiment, the metal alkyl can comprise,consist essentially of, or consist of, a non-halide metal alkyl, a metalalkyl halide, or any combination thereof; alternatively, a non-halidemetal alkyl; or alternatively, a metal alkyl halide.

In an embodiment, the metal of the metal alkyl can comprise, consistessentially of, or consist of, a group 1, 2, 11, 12, 13, or 14 metal; oralternatively, a group 13 or 14 metal; or alternatively, a group 13metal. In some embodiments, the metal of the metal alkyl (non-halidemetal alkyl or metal alkyl halide) can be lithium, sodium, potassium,rubidium, cesium, beryllium, magnesium, calcium, strontium, barium,zinc, cadmium, boron, aluminum, or tin; alternatively, lithium, sodium,potassium, magnesium, calcium, zinc, boron, aluminum, or tin;alternatively, lithium, sodium, or potassium; alternatively, magnesium,calcium; alternatively, lithium; alternatively, sodium; alternatively,potassium; alternatively, magnesium; alternatively, calcium;alternatively, zinc; alternatively, boron; alternatively, aluminum; oralternatively, tin. In some embodiments, the metal alkyl (non-halidemetal alkyl or metal alkyl halide) can comprise, consist essentially of,or consist of, a lithium alkyl, a sodium alkyl, a magnesium alkyl, aboron alkyl, a zinc alkyl, or an aluminum alkyl. In some embodiments,the metal alkyl (non-halide metal alkyl or metal alkyl halide) cancomprise, consist essentially of, or consist of, an aluminum alkyl.

In an embodiment, the aluminum alkyl can be a trialkylaluminum, analkylaluminum halide, an alkylaluminum alkoxide, an aluminoxane, or anycombination thereof. In some embodiments, the aluminum alkyl can be atrialkylaluminum, an alkylaluminum halide, an aluminoxane, or anycombination thereof; or alternatively, a trialkylaluminum, analuminoxane, or any combination thereof. In other embodiments, thealuminum alkyl can be a trialkylaluminum; alternatively, analkylaluminum halide; alternatively, an alkylaluminum alkoxide; oralternatively, an aluminoxane.

In a non-limiting embodiment, the aluminoxanecan have a repeating unitcharacterized by the

wherein R¹ is a linear or branched alkyl group. Alkyl groups for metalalkyls have been independently described herein and can be utilizedwithout limitation to further describe the aluminoxanes having FormulaI. Generally, n of Formula I is greater than 1; or alternatively,greater than 2. In an embodiment, n can range from 2 to 15; oralternatively, range from 3 to 10.

In an aspect, each halide of any metal alkyl halide disclosed herein canindependently be fluoride, chloride, bromide, or iodide; alternatively,chloride, bromide, or iodide. In an embodiment, each halide of any metalalkyl halide disclosed herein can be fluoride; alternatively, chloride;alternatively, bromide; or alternatively, iodide.

In an aspect, each alkyl group of any metal alkyl disclosed herein(non-halide metal alkyl or metal alkyl halide) independently can be a C₁to C₂₀ alkyl group; alternatively, a C₁ to C₁₀ alkyl group; oralternatively, a C₁ to C₆ alkyl group. In an embodiment, each alkylgroup(s) independently can be a methyl group, an ethyl group, a propylgroup, a butyl group, a pentyl group, a hexyl group, a heptyl group, oran octyl group; alternatively, a methyl group, a ethyl group, a butylgroup, a hexyl group, or an octyl group. In some embodiments, alkylgroup independently can be a methyl group, an ethyl group, an n-propylgroup, an n-butyl group, an iso-butyl group, an n-hexyl group, or ann-octyl group; alternatively, a methyl group, an ethyl group, an n-butylgroup, or an iso-butyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an n-propyl group;alternatively, an n-butyl group; alternatively, an iso-butyl group;alternatively, an n-hexyl group; or alternatively, an n-octyl group.

In an aspect, alkoxide group of any metal alkyl alkoxide disclosedherein independently can be a C₁ to C₂₀ alkoxy group; alternatively, aC₁ to C₁₀ alkoxy group; or alternatively, a C₁ to C₆ alkoxy group. In anembodiment, each alkoxide group of any metal alkyl alkoxide disclosedherein independently can be a methoxy group, an ethoxy group, a propoxygroup, a butoxy group, a pentoxy group, a hexoxy group, a heptoxy group,or an octoxy group; alternatively, a methoxy group, a ethoxy group, abutoxy group, a hexoxy group, or an octoxy group. In some embodiments,each alkoxide group of any metal alkyl alkoxide disclosed hereinindependently can be a methoxy group, an ethoxy group, an n-propoxygroup, an n-butoxy group, an iso-butoxy group, an n-hexoxy group, or ann-octoxy group; alternatively, a methoxy group, an ethoxy group, ann-butoxy group, or an iso-butoxy group; alternatively, a methoxy group;alternatively, an ethoxy group; alternatively, an n-propoxy group;alternatively, an n-butoxy group; alternatively, an iso-butoxy group;alternatively, an n-hexoxy group; or alternatively, an n-octoxy group.

In a non-limiting embodiment, useful metal alkyls can include methyllithium, n-butyl lithium, sec-butyl lithium, tert-butyl lithium, diethylmagnesium, di-n-butylmagnesium, ethylmagnesium chloride,n-butylmagnesium chloride, and diethyl zinc.

In a non-limiting embodiment, useful trialkylaluminum compounds caninclude trimethylaluminum, triethylaluminum, tripropylaluminum,tributylaluminum, trihexylaluminum, trioctylaluminum, or mixturesthereof. In some non-limiting embodiments, trialkylaluminum compoundscan include trimethylaluminum, triethylaluminum, tripropylaluminum,tri-n-butylaluminum, tri-isobutylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof; alternatively,triethylaluminum, tri-n-butylaluminum, tri-isobutylaluminum,trihexylaluminum, tri-n-octylaluminum, or mixtures thereof;alternatively, triethylaluminum, tri-n-butylaluminum, trihexylaluminum,tri-n-octylaluminum, or mixtures thereof. In other non-limitingembodiments, useful trialkylaluminum compounds can includetrimethylaluminum; alternatively, triethylaluminum; alternatively,tripropylaluminum; alternatively, tri-n-butylaluminum; alternatively,tri-isobutylaluminum; alternatively, trihexylaluminum; or alternatively,tri-n-octylaluminum.

In a non-limiting embodiment, useful alkylaluminum halides can includediethylaluminum chloride, diethylaluminum bromide, ethylaluminumdichloride, ethylaluminum sesquichloride, and mixtures thereof. In somenon-limiting embodiments, useful alkylaluminum halides can includediethylaluminum chloride, ethylaluminum dichloride, ethylaluminumsesquichloride, and mixtures thereof. In other non-limiting embodiments,useful alkylaluminum halides can include diethylaluminum chloride;alternatively, diethylaluminum bromide; alternatively, ethylaluminumdichloride; or alternatively, ethylaluminum sesquichloride.

In a non-limiting embodiment, useful aluminoxanes can includemethylaluminoxane (MAO), ethylaluminoxane, modified methylaluminoxane(MMAO), n-propylaluminoxane, iso-propyl-aluminoxane, n-butylaluminoxane,sec-butylaluminoxane, iso-butylaluminoxane, t-butyl aluminoxane,1-pentylaluminoxane, 2-pentylaluminoxane, 3-pentylaluminoxane,iso-pentylaluminoxane, neopentylaluminoxane, or mixtures thereof; Insome non-limiting embodiments, useful aluminoxanes can includemethylaluminoxane (MAO), modified methylaluminoxane (MMAO), isobutylaluminoxane, t-butyl aluminoxane, or mixtures thereof. In othernon-limiting embodiments, useful aluminoxanes can includemethylaluminoxane (MAO); alternatively, ethylaluminoxane; alternatively,modified methylaluminoxane (MMAO); alternatively, n-propylaluminoxane;alternatively, iso-propylaluminoxane; alternatively, n-butylaluminoxane;alternatively, sec-butylaluminoxane; alternatively,iso-butylaluminoxane; alternatively, t-butyl aluminoxane; alternatively,1-pentylaluminoxane; alternatively, 2-pentylaluminoxane; alternatively,3-pentylaluminoxane; alternatively, iso-pentyl-aluminoxane; oralternatively, neopentylaluminoxane.

In an aspect, the metal alkyl and N²-phosphinyl amidine metal saltcomplex may be combined in any ratio that forms an active catalystsystem. In an embodiment, the metal of the metal alkyl to the metal ofthe N²-phosphinyl amidine metal salt complex molar ratio can be greaterthan or equal to 5:1; alternatively, greater than or equal to 10:1;alternatively, greater than or equal to 25:1; alternatively, greaterthan or equal to 50:1; or alternatively, greater than or equal to 100:1.In some embodiments, the metal of the metal alkyl to the metal of theN²-phosphinyl amidine metal salt complex molar ratio can range from 5:1to 100,000:1; alternatively, range from 10:1 to 50,000:1; alternatively,range from 25:1 to 10,000:1; alternatively, range from 50:1 to 5,000:1;or alternatively, range from 100:1 to 2,500:1. When a metal alkyl havinga specific metal and an N²-phosphinyl amidine metal salt complex havinga specific metal is utilized the metal of the metal alkyl to the metalof the N²-phosphinyl amidine metal salt complex molar ratio can bestated as a specific metal of the metal alkyl to specific metal of theN²-phosphinyl amidine metal salt complex molar ratio. For example, whenthe metal alkyl is an alkylaluminum compound (e.g. trialkylaluminum,alkylaluminum halide, alkylaluminum alkoxide, and/or aluminoxane) andthe N²-phosphinyl amidine metal salt complex is an N²-phosphinyl amidinechromium salt complex, the metal of the metal alkyl to metal of themetal salt can be an aluminum to chromium molar ratio. In somenon-limiting embodiments, the aluminum to chromium molar ratio can begreater than or equal to 5:1; alternatively, greater than or equal to10:1; alternatively, greater than or equal to 25:1; alternatively,greater than or equal to 50:1; alternatively, greater than or equal to100:1; alternatively, range from 5:1 to 100,000:1; alternatively, rangefrom 10:1 to 50,000:1; alternatively, range from 25:1 to 10,000:1;alternatively, range from 50:1 to 5,000:1; or alternatively, range from100:1 to 2,500:1.

In another aspect, the metal alkyl, metal salt, and N²-phosphinylamidine compound can be combined in any ratio that forms an activecatalyst system. Generally the ratio of the components of the catalystsystem comprising, consisting essentially of, or consisting of a metalalkyl, metal salt, and N²-phosphinyl amidine compound can be provided asa molar ratio of the metal of the metal alkyl to metal of the metal saltand an equivalent ratio of the N²-phosphinyl amidine compound to metalsalt.

In an embodiment, the metal of the metal alkyl to the metal of the metalsalt molar ratio can be greater than or equal to 5:1; alternatively,greater than or equal to 10:1; alternatively, greater than or equal to25:1; alternatively, greater than or equal to 50:1; or alternatively,greater than or equal to 100:1. In some embodiments, the metal of themetal alkyl to the metal of the metal salt molar ratio can range from5:1 to 100,000:1; alternatively, ranges from 10:1 to 50,000:1;alternatively, ranges from 25:1 to 10,000:1; alternatively, ranges from50:1 to 5,000:1; or alternatively, ranges from 100:1 to 2,500:1. When ametal alkyl having a specific metal and a metal salt having a specificmetal is utilized the metal of the metal alkyl to the metal of the metalsalt molar ratio can be stated as a specific metal of the metal alkyl tospecific metal of the metal salt molar ratio. For example, when themetal alkyl is an alkylaluminum compound (e.g. trialkylaluminum,alkylaluminum halide, alkylaluminum alkoxide, and/or aluminoxane) andthe metal salt is a chromium salt, the metal of the metal alkyl to metalof the metal salt can be an aluminum to chromium molar ratio. In somenon-limiting embodiments, the aluminum to chromium molar ratio can begreater than or equal to 5:1; alternatively, greater than or equal to10:1; alternatively, greater than or equal to 25:1; alternatively,greater than or equal to 50:1; alternatively, greater than or equal to100:1; alternatively, range from 5:1 to 100,000:1; alternatively, rangefrom 10:1 to 50,000:1; alternatively, range from 25:1 to 10,000:1;alternatively, range from 50:1 to 5,000:1; or alternatively, range from100:1 to 2,500:1

In an embodiment, the N²-phosphinyl amidine compound to metal saltequivalent ratio can be greater than or equal to 0.8:1; alternatively,greater than or equal to 0.9:1; or alternatively, greater than or equalto 0.95:1; or alternatively, greater than or equal to 0.98:1. In someembodiments, the N²-phosphinyl amidine compound to metal salt equivalentratio can be range from 0.8:1 to 5:1; alternatively, range from 0.9:1 to4:1; or alternatively, range from 0.95:1 to 3:1; or alternatively, rangefrom 0.98:1 to 2.5:1. In other embodiments, the N²-phosphinyl amidinecompound to metal salt equivalent ratio can be about 1:1.

In an aspect, this disclosure relates to a method of preparing anN²-phosphinyl amidine compound and/or an N²-phosphinyl amidine metalsalt complex. N²-phosphinyl amidine compounds and N²-phosphinyl amidinemetal salt complexes are generally described herein and methods ofpreparing them can be generally applied to any N²-phosphinyl amidinecompound and/or N²-phosphinyl amidine metal salt complex describedherein.

In an aspect, this disclosure relates to a method of preparing anN²-phosphinyl amidine compound. Generally, the method of preparing anN²-phosphinyl amidine compound can comprise: a) contacting a phosphinehalide with a metal amidinate, and b) forming the N²-phosphinylamidinate. Generally, the N²-phosphinyl amidine compound can be formedunder conditions capable of forming an N²-phosphinyl amidine group. Insome embodiments, the N²-phosphinyl amidine compound can be isolated;alternatively, purified; or alternatively, isolated and purified. In anembodiment, the N²-phosphinyl amidine compound can have any Structuredescribed herein.

Generally, the metal amidinate utilized in the method of preparing theN²-phosphinyl amidine compound can have Structure MAM1, MAM2, MAM3,MAM4, MAM5, MAM6, MAM7, MAM8, MAM9, MAM10, MAM11, MAM13, MAM15, MAM16,MAM18, or MAM20; alternatively, Structure MAM1, MAM2, MAM3, MAM4, orMAM5; alternatively, Structure MAM6, MAM7, MAM8, MAM9, or MAM10;alternatively, Structure MAM11, MAM13, or MAM15; alternatively,Structure MAM16, MAM18, or MAM20; alternatively, Structure MAM1;alternatively, Structure MAM2; alternatively, Structure MAM3;alternatively, Structure MAM4; alternatively, Structure MAM5;alternatively, Structure MAM11; alternatively, MAM6; alternatively,MAM7; alternatively, MAM8; alternatively, MAM9; alternatively, MAM10;alternatively, Structure MAM13; alternatively Structure MAM15;alternatively, MAM16; alternatively, MAM18; or alternatively, MAM20. Inan embodiment, the N²-phosphinyl amidine metal salt complex comprisingonly one N²-phosphinyl amidine group complexed to a metal salt can becharacterized by having the Structure MAM1, MAM6, MAM11, or MAM16;alternatively, Structure MAM1 or MAM6; alternatively, Structure MAM11 orMAM16; alternatively, Structure MAM1 or MAM11; or alternatively,Structure MAM6 or MAM16. In an embodiment, the N²-phosphinyl amidinemetal salt complex comprising only two N²-phosphinyl amidine groupscomplexed to a metal salt can be characterized by having Structure MAM2,MAM3, MAM8, MAM13, or MAM18; alternatively, Structure MAM2, MAM3, orMAM8; alternatively, Structure MAM13, or MAM18; alternatively, StructureMAM2 or MAM3; alternatively, Structure MAM3 or MAM13; or alternatively,Structure MAM8 or MAM18. In other embodiments, N²-phosphinyl amidinemetal salt complex compounds having at least one N²-phosphinyl amidinegroup complexed to a metal salt can be characterized by having theStructure MAM4, MAM5, MAM9, MAM10, MAM15, or MAM20; alternatively,Structure MAM4, MAM5, MAM9, or MAM10; alternatively, Structure MAM15, orMAM20; alternatively, Structure MAM4 or MAM5; alternatively, StructureMAM9 or MAM10; alternatively, Structure MAM5 or MAM15; or alternatively,Structure MAM10 or MAM20.

Generally, the metal amidinate structures prefaced with the designationMAM correspond with the N2-phosphinyl amidine structures prefaced withthe designation NP having the same number designation. R1, R2, R3, D1,D2, L¹, L², L³, Q¹, q, and r within metal amidine Structures MAM1-MAM10,MAM11, MAM13, MAM15, MAM16, MAM18, and/or MAM20 are independentlydescribed as features of the N2-phosphinyl amidine compound StructuresNP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20. Since metal amidineStructures MAM1-MAM10, MAM11, MAM13, MAM15, MAM16, MAM18, and/or MAM20are utilized to prepare embodiments of N2-phosphinyl amidine compoundshaving Structures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20,the R¹, R², R³, D1, D2, L¹, L², L³, Q¹, q, and r descriptions for theN2-phosphinyl amidine compounds may be utilized without limitation tofurther describe metal amidine Structures MAM1-MAM10, MAM11, MAM13,MAM15, MAM16, MAM18, and/or MAM20.

In an embodiment, the phosphine halide utilized in the method to preparethe N²-phosphinyl amidine compound can have the Structure PH1.

R⁴ and R⁵ of the phosphine halide having Structure PH1 correspond to R⁴and R⁵ of the embodiments of the N²-phosphinyl amidine compoundsStructures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20. Sincethe phosphine halide having Structure PH1 is utilized to prepareembodiments of N²-phosphinyl amidine compounds having StructuresNP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20, the R⁴ and R⁵descriptions for the N²-phosphinyl amidine compounds can be utilizedwithout limitation to further describe the phosphine halide havingStructures PH1. In an embodiment, X¹ of the phosphine halide can befluoro, chloro, bromo, or iodo; alternatively, fluoro; alternatively,chloro; alternatively, bromo; or alternatively, iodo. Phosphine halidesare disclosed herein and can be utilized, without limitation, to furtherdescribe the method to prepare the N²-phosphinyl amidine compound.

Generally, the phosphine halide and the metal amidinate can be combinedat a phosphine halide to metal amidinate equivalent ratio of at least0.9:1. In some embodiments, the phosphine halide and the metal amidinatecan be combined at a phosphine halide to metal amidinate equivalentratio of at least 0.95:1; alternatively, of at least 0.975:1; oralternatively, of at least 0.99:1. In some embodiments, the phosphinehalide and the metal amidinate can be combined at a phosphine halide tometal amidinate equivalent ratio ranging from 0.9:1 to 1.25:1;alternatively, ranging from 0.95:1 to 1.20:1; alternatively, rangingfrom 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to 1.10:1.In other embodiments, the phosphine halide and the metal amidinate canbe combined at a phosphine halide to metal amidinate equivalent ratio ofabout 1:1.

In an embodiment, the conditions capable of forming an N²-phosphinylamidine can include a reaction temperature of at least 0° C.;alternatively, of at least 5° C.; alternatively, of at least 10° C.; oralternatively, of at least 15° C. In some embodiments, the conditionscapable of forming an N²-phosphinyl amidine can include a reactiontemperature ranging from 0° C. to 60° C.; alternatively, ranging from 5°C. to 50° C.; alternatively, ranging from 10° C. to 45° C.; oralternatively, ranging from 15° C. to 40° C. In an embodiment, theconditions capable of forming an N²-phosphinyl amidine can include areaction time of at least 5 minutes; alternatively, of at least 10minutes; alternatively, of at least 15 minutes; or alternatively, of atleast 20 minutes. In some embodiments, the conditions capable of formingan N²-phosphinyl amidine can include a reaction time ranging from 5minutes to 6 hours; alternatively, ranging from 10 minutes to 5 hours;alternatively, ranging from 15 minutes to 4.5 hours; or alternatively,ranging from 20 minutes to 4 hours.

In an embodiment, the phosphine halide and the metal amidinate can becontacted in an aprotic solvent. In some embodiments, the phosphinehalide and the metal amidinate can be contacted in a polar aproticsolvent. Aprotic solvents which can be utilized include hydrocarbonsolvents and ether solvents. Polar aprotic solvents which can beutilized include ether solvents. Solvents are generally disclosed hereinand any general or specific aprotic solvent and/or polar aprotic solventdescribed herein can be utilized to further describe the method ofpreparing an N²-phosphinyl amidine compound comprising contacting aphosphine halide with a metal amidinate and forming the N²-phosphinylamidinate.

In an embodiment, the N²-phosphinyl amidine compound can be utilizedwithout further isolation or purification. In some embodiments, theN²-phosphinyl amidine compound can be isolated; or alternatively,isolated and purified. In an embodiment, wherein the N²-phosphinylamidine compound can be prepared in a solvent (aprotic or polaraprotic), the method to prepare the N²-phosphinyl amidine compound caninclude a step of isolating the N²-phosphinyl amidine compound byevaporating the solvent. In an embodiment wherein the N²-phosphinylamidine compound can prepared in a solvent (aprotic or polar aprotic),the method to prepare the N²-phosphinyl amidine compound can include thestep of isolating the N²-phosphinyl amidine compound by filtering thesolution to remove particulate materials and/or byproducts of thereaction and evaporating the solvent. In embodiments, the method toprepare the N²-phosphinyl amidine compound can include a purificationstep wherein the N²-phosphinyl amidine compound can be purified bydissolving the N²-phosphinyl amidine compound in a solvent and filteringthe solution to remove particulate materials and/or byproducts of thereaction. The solvent utilized to purify the N²-phosphinyl amidinecompound can be the same solvent utilized to form the N²-phosphinylamidine compound or it can be different than the solvent utilized toform the N²-phosphinyl amidine compound. In some embodiments, the methodto prepare the N²-phosphinyl amidine compound can include a purificationstep of washing the N²-phosphinyl amidine compound with a solvent. Inother embodiments, the method to prepare the N²-phosphinyl amidinecompound can include a purification step of recrystallizing theN²-phosphinyl amidine compound.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g., at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

In an aspect, the metal amidinate utilized in the method to prepare theN²-phosphinyl amidine can be formed by a) contacting an amidine compound(non-metallic) having an N² hydrogen atom with a metallic compoundcapable of abstracting the hydrogen atom from the amidine compound; andb) forming the metal amidinate. Generally, the metal amidinate can beformed under conditions capable of forming a metal amidinate. In someembodiments, the metal amidinate can be isolated; alternatively,purified; or alternatively, isolated and purified.

In an embodiment, the amidine compound (non-metallic) can have StructureAM1, AM2, AM3, AM4, AM5, AM6, AM7, AM8, AM9, AM10, AM11, AM13, AM15,AM16, AM18, or AM20; alternatively, Structure AM1, AM2, AM3, AM4, orAM5; alternatively, AM6, AM7, AM8, AM9, or AM10; alternatively, AM11,AM13, or AM15; alternatively, AM16, AM18, or AM20; alternatively,Structure AM1; alternatively, Structure AM2; alternatively, StructureAM3; alternatively, Structure AM4; alternatively, Structure AM5;alternatively, Structure AM11; alternatively, Structure AM6;alternatively, Structure AM7; alternatively, Structure AM8;alternatively, Structure AM9; alternatively, Structure AM10;alternatively, Structure AM11; alternatively, Structure AM13;alternatively, Structure AM15; alternatively, AM16; alternatively, AM18;or alternatively, AM20. In an embodiment, the amidine compound(non-metallic) comprising only one N²-phosphinyl amidine group complexedto a metal salt can be characterized by having the Structure AM1, AM6,AM11, or AM16; alternatively, Structure AM1 or AM6; alternatively,Structure AM11 or AM16; alternatively, Structure AM1 or AM11; oralternatively, Structure AM6 or AM16. In an embodiment, the amidinecompound (non-metallic) comprising only two N²-phosphinyl amidine groupscomplexed to a metal salt can be characterized by having Structure AM2,AM3, AM8, AM13, or AM18; alternatively, Structure AM2, AM3, or AM8;alternatively, Structure AM13, or AM18; alternatively, Structure AM2 orAM3; alternatively, Structure AM3 or AM13; or alternatively, StructureAM8 or AM18. In other embodiments, the amidine compound (non-metallic)having at least one N²-phosphinyl amidine group complexed to a metalsalt can be characterized by having the Structure AM4, AM5, AM9, AM10,AM15, or AM20; alternatively, Structure AM4, AM5, AM9, or AM10;alternatively, Structure AM15, or AM20; alternatively, Structure AM4 orAM5; alternatively, Structure AM9 or AM10; alternatively, Structure AM5or AM15; alternatively, Structure AM10 or AM20. In some embodiments, theamidine compounds may have only one N² hydrogen atom (i.e., R³ is anon-hydrogen group in the amidine compounds). In other embodiments, theamidine may have two N² hydrogen atoms (i.e., R³ is a non-hydrogen groupin the amidine compounds).

Generally, the amidine structure prefaced with AM corresponds to themetal amidinate structure prefaced with MAM having the same numberdesignation. However, it should be noted that methods described hereinprovide for the conversion of amidine compounds having StructuresAM6-AM10, AM16, AM18, and/or AM20 (wherein R³ is hydrogen) into amidinecompounds having Structures AM1-AM5, AM11, AM13, and/or AM15 (wherein R³is not hydrogen), respectively. R¹, R², R³, D¹, D², L¹, L², L³, Q¹, q,and r within amidine compound Structures AM1-AM10, AM11, AM13, AM15,AM16, AM18, and/or AM20 are independently described as features of theN2-phosphinyl amidine compound Structures NP1—NP10, NP11, NP13, NP15,NP16, NP18, and/or NP20. Since amidine Structures AM1-AM10, AM11, AM13,AM15, AM16, AM18, and/or AM20 can be utilized to prepare embodiments ofN2-phosphinyl amidine compounds having Structures NP1—NP10, NP11, NP13,NP15, NP16, NP18, and/or NP20, the R¹, R², R³, D¹, D², L¹, L², L³, Q¹,q, and r descriptions for the N2-phosphinyl amidine compounds can beutilized without limitation to further describe the amidine StructuresAM1-AM10, AM11, AM13, AM15, AM16, AM18, and/or AM20.

In an embodiment, the metal compound capable of abstracting the protonfrom the amidine compound (non-metallic) can be a metal hydride or ametal alkyl; alternatively, a metal hydride; or alternatively, a metalalkyl. In an embodiment the metal hydride can be sodium hydride, calciumhydride, lithium aluminum hydride or sodium borohydride; alternatively,sodium hydride or calcium hydride; alternatively, lithium aluminumhydride or sodium borohydride; alternatively, sodium hydride;alternatively, calcium hydride; alternatively, lithium aluminum hydride;or alternatively, sodium borohydride. Metal alkyl compounds aredescribed herein and can be utilized, without limitation, as the metalalkyl for abstracting the proton from the amidine compound(non-metallic). Particularly useful metal alkyls for abstracting theproton from the amidine compound (non-metallic) can be Group 1 metalhydrides or Group 1 metal alkyls; alternatively, Group 1 metal hydrides;or alternatively, Group 1 metal alkyls. In an embodiment, the metalalkyl can be a lithium alkyl, a sodium alkyl, or a potassium alkyl;alternatively, a lithium alkyl or a sodium alkyl; alternatively, alithium alkyl; alternatively, a sodium alkyl; or alternatively, apotassium alkyl. Alkyl groups for the metal alkyl are described hereinand can be utilized without limitation to further describe the metalalkyls which can be contacted with the amidine compound. In someexemplary embodiments, the metal alkyl can be methyl lithium, n-butyllithium, sec-butyl lithium, or tert-butyl lithium; alternatively, methyllithium; alternatively, n-butyl lithium; alternatively, sec-butyllithium; or alternatively, tert-butyl lithium.

Generally, the amidine compound (non-metallic) and the metal compoundcan be combined in an amidine compound to metal compound equivalentratio of at least 0.9:1. In an embodiment, the amidine compound(non-metallic) and the metal compound can be combined in an amidinecompound to metal compound equivalent ratio of at least 0.95:1;alternatively, of at least 0.975:1; or alternatively, of at least0.99:1. In some embodiments, the amidine compound (non-metallic) and themetal compound can be combined in an amidine compound and metal compoundequivalent ratio ranging from 0.9:1 to 1.25:1; alternatively, rangingfrom 0.95:1 to 1.20:1; alternatively, ranging from 0.975:1 to 1.15:1; oralternatively, ranging from 0.99:1 to 1.10:1. In other embodiments, theamidine compound (non-metallic) and the metal compound can be combinedin an amidine compound to metal compound equivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming the metal amidinatecan include a temperature of at least −45° C.; alternatively, of atleast −30° C.; alternatively, of at least −25° C.; or alternatively, ofat least −20° C. In some embodiments, the reaction conditions capable offorming a metal amidinate can include a temperature ranging from −45° C.to 60° C.; alternatively, ranging from −30° C. to 50° C.; alternatively,ranging from −25° C. to 45° C.; or alternatively, ranging from −20° C.to 40° C.

In some embodiments, the conditions capable of forming the metalamidinate can include an initial metal compound and amidine compoundcontact temperature and a second temperature to form the metalamidinate. It should be noted the when the conditions capable of formingthe metal amidinate is described as occurring at two temperatures (onefor the contact of the metal compound and the amidine compound and onefor the formation of the metal amidinate) that this description does notexclude the prospect that metal amidinate can be formed at the contacttemperature. The description just relates that, in some embodiments, themetal amidinate formation may proceed better when the initial contactbetween the metal compound and amidine compound is performed at onetemperature and the formation of the metal amidinate is completed at asecond different temperature.

In an embodiment, the metal compound and amidine compound can becontacted at a temperature ranging from −45° C. to 20° C.;alternatively, ranging from −30° C. to 15° C.; alternatively, rangingfrom −25° C. to 45° C.; or alternatively, ranging from −20° C. to 40° C.In an embodiment, the metal amidinate can be formed at a temperatureranging from 0° C. to 20° C.; alternatively, ranging from 5° C. to 15°C.; alternatively, ranging from 10° C. to 45° C.; or alternatively,ranging from 15° C. to 40° C.

In an embodiment, the conditions capable of forming the metal amidinatecan include a metal amidinate formation time of at least 5 minutes;alternatively, of at least 10 minutes; alternatively, of at least 15minutes; or alternatively, of at least 20 minutes. In some embodiments,the conditions capable of forming the metal amidinate can include ametal amidinate formation time ranging from 5 minutes to 6 hours;alternatively, ranging from 10 minutes to 5 hours; alternatively,ranging from 15 minutes to 4.5 hours; or alternatively, ranging from 20minutes to 4 hours.

In an embodiment, the metal compound and the amidine compound(non-metallic) can be contacted in an aprotic solvent. In someembodiments, the metal compound and the amidine compound (non-metallic)can be contacted in a polar aprotic solvent. Aprotic solvents which canbe utilized include hydrocarbon solvents and ether solvents. Polaraprotic solvents which can be utilized include ether solvents. Solventsare generally disclosed herein and any general or specific aproticsolvent and/or polar aprotic solvent described herein can be utilized tofurther describe the method of preparing the metal amidinate bycontacting a metal compound and an amidine compound and forming a metalamidinate.

In an embodiment, the metal amidinate can be utilized without furtherisolation or purification. In some embodiments, the metal amidinate canbe isolated; alternatively, purified; or alternatively, isolated andpurified. In an embodiment, the method to prepare the metal amidinatecan include a step of isolating the metal amidinate by filtering themetal amidate from the solution. In some embodiments, the method toprepare the metal amidinate can include a step of purifying the metalamidinate by washing the metal amidinate with a solvent. Generally, thewashing solvent can be an aprotic solvent. In other embodiments, thewashing solvent can be a polar aprotic solvent. In other embodiments,the washing solvent can be a non-polar aprotic solvent.

In an aspect, the metal amidinate which can be utilized to prepare theN²-phosphinyl amidine can be prepared by a method comprising: a)contacting a metal amide and a nitrile; and b) forming the metalamidinate. Generally, the metal amidinate can be formed under conditionscapable of forming a metal amidinate. In some embodiments, the metalamidinate can be isolated; alternatively, purified; or alternatively,isolated and purified. It should be noted that this method prepares ametal amidinate having a N² hydrogen atom (i.e., R³ is hydrogen). Othermethods for preparing metal amidinates having a non-hydrogen R³ groupare disclosed herein.

In an embodiment, the metal amide has Structures MA1, MA2, MA3, or MA4;alternatively, MA1; alternatively, MA2; alternatively, MA3; oralternatively, MA4.

R¹—NHM^(A) M^(A)HN—L¹—NHM^(A) D¹ NHM^(A))_(q) Q¹—L³—NHM^(A) StructureStructure Structure Structure MA1 MA2 MA3 MA4

In an embodiment, the nitrile may have Structure N¹, N², or N3;alternatively, N1; alternatively, N2; or alternatively, N3.

R²—C≡N N≡C—L²—C≡N D² C≡N)_(r) Structure N1 Structure N2 Structure N3

Generally, utilizing the present disclosure, one can readily recognizethe metal amide structure and the nitrile structure necessary to producea particular metal amidinate. For example, a metal amidinate havingStructure AM6 can be prepared from the metal amide having Structure MA1and the nitrile having Structure N¹, a metal amidinate having StructureAM7 can be prepared from the metal amide having Structure MA2 and thenitrile having Structure N¹, a metal amidinate having Structure AM8 canbe prepared from the metal amide having Structure MA1 and the nitrilehaving Structure N2, a metal amidinate having Structure AM9 can beprepared from the metal amide having Structure MA3 and the nitrilehaving Structure N¹, a metal amidinate having Structure AM10 can beprepared from the metal amide having Structure MA1 and the nitrilehaving Structure N3, a metal amidinate having Structure AM16 can beprepared from the metal amide having Structure MA4 and the nitrilehaving Structure N¹, a metal amidinate having Structure AM18 can beprepared from the metal amide having Structure MA4 and the nitrilehaving Structure N2, and a metal amidinate having Structure AM20 can beprepared from the metal amide having Structure MA4 and the nitrilehaving Structure N3. R¹, R², R³, R⁴, R⁵, D¹, D², L¹, L², L³, Q¹, q, andr within metal amide Structures MA1-MA4 and nitrile Structures N1-N3 areindependently described as features of the N2-phosphinyl amidinecompounds Structures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and/orNP20. Since the metal amides having Structures MA1-MA4 and the nitrileshaving Structures N1-N3 are utilized to ultimately prepare embodimentsof N2-phosphinyl amidine compounds having Structures NP1—NP10, NP11,NP13, NP15, NP16, NP18, and/or NP20, the R¹, R², R³, R⁴, R⁵, D¹, D², L¹,L², L³, Q¹, q, and r descriptions for the N2-phosphinyl amidinecompounds can be utilized without limitation to further describe themetal amides having Structures MA1-MA4 and the nitriles havingStructures N1-N3. General and specific metal amides (or the amines fromwhich they are derived) and nitriles are provided herein and can beutilized without limitation to further describe the method of preparingthe herein disclosed metal amidinates.

Generally, the nitrile and the metal amide can be combined in a nitrileto metal amide equivalent ratio of at least 0.9:1. In an embodiment, thenitrile and the metal amide can be combined in a nitrile to metal amideequivalent ratio of at least 0.95:1; alternatively, of at least 0.975:1;or alternatively, of at least 0.99:1. In some embodiments, the nitrileand the metal amide can be combined in a nitrile to metal amideequivalent ratio ranging from 0.9:1 to 1.25:1; alternatively, rangingfrom 0.95:1 to 1.20:1; alternatively, ranging from 0.975:1 to 1.15:1; oralternatively, ranging from 0.99:1 to 1.10:1. In other embodiments, thenitrile and the metal amide can be combined in a metal amide to nitrileequivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming the metal amidinatecan include a reaction temperature of at least 10° C.; alternatively, ofat least 15° C.; alternatively, of at least 20° C.; or alternatively, ofat least 25° C. In some embodiments, the conditions capable of formingthe metal amidinate can include a reaction temperature ranging from 10°C. to 100° C.; alternatively, ranging from 15° C. to 90° C.;alternatively, ranging from 20° C. to 85° C.; or alternatively, rangingfrom 25° C. to 80° C. In an embodiment, the conditions capable offorming the metal amidinate can include a reaction time of at least 15minutes; alternatively, of at least 30 minutes; alternatively, of atleast 45 minutes; or alternatively, of at least 1 hour. In someembodiments, the conditions capable of forming the metal amidinate caninclude a reaction time ranging from 15 minutes to 36 hours;alternatively, ranging from 30 minutes to 30 hours; alternatively,ranging from 45 minutes to 24 hours; or alternatively, ranging from 1hour to 18 hours.

In an embodiment, the nitrile and the metal amide can be contacted in anaprotic solvent. In some embodiments, the nitrile and the metal amidecan be contacted in a polar aprotic solvent. Aprotic solvents which canbe utilized include hydrocarbon solvents and ether solvents. Polaraprotic solvents which may be utilized include ether solvents. Solventsare generally disclosed herein and any general or specific aproticsolvent and/or polar aprotic solvent described herein can be utilized tofurther describe the method of preparing the metal amidinate bycontacting a nitrile and a metal amide and forming the metal amidinate.

In an embodiment, the metal amidinate can be utilized without furtherisolation or purification. In some embodiments, the metal amidinate canbe isolated; alternatively, purified; or alternatively, isolated andpurified. In an embodiment, the method to prepare the metal amidinatecan include a step of isolating the metal amidinate by filtering themetal amidate from the solution. In some embodiments, the method toprepare the metal amidinate can include a step of purifying the metalamidinate washing the metal amidinate with a solvent. Generally, thewashing solvent can be an aprotic solvent. In other embodiments, thewashing solvent can be a polar aprotic solvent. In other embodiments,the washing solvent can be a non-polar aprotic solvent.

In an aspect, the amidine compound which can be utilized to form theN²-phosphinyl amidine compound can be prepared by a method comprising:a) contacting a metal amide and a nitrile; b) forming the metalamidinate; and c) neutralizing the formed metal amidinate with a proticcompound to form a non-metal amidine compound. Steps a) and b) of thismethod are the same as the method of preparing a metal amidinatecomprising contacting a metal amide and a nitrile and forming the metalamidinate. As such, embodiments relating to the steps of contacting ametal amide and a nitrile and forming the metal amidinate describedherein can be utilized without limitation to further describe the methodof making an amidinate compound comprising; a) contacting a metal amideand a nitrile; b) forming the metal amidinate; and c) neutralizing theformed metal amidinate. In some embodiments, the non-metal amidinecompound can be isolated; alternatively, purified; or alternatively,isolated and purified.

In an embodiment, the protic compound can be any compound capable ofproviding a proton to neutralize the metal amidinate. In someembodiments, the protic compound can be Brønsted acid. In otherembodiments, the protic compound can be water, a mineral acid, acarboxylic acid, an alcohol, or an amine hydrohalide; alternatively,water; alternatively, a mineral acid; alternatively, a carboxylic acid;alternatively, an alcohol; or alternatively, an amine hydrohalide. In anembodiment, the mineral acid can be hydrochloric acid, hydrobromic acid,sulfuric acid, nitric acid, phosphoric acid, or boric acid;alternatively, hydrochloric acid; alternatively, sulfuric acid;alternatively, nitric acid; alternatively, phosphoric acid; oralternatively, boric acid. In an embodiment, the carboxylic acid can bea C₁ to C₅ carboxylic acid. In some embodiments, the carboxylic acid canbe formic acid, acetic acid, propionic acid, or butyric acid;alternatively, formic acid or acetic acid; alternatively, formic acid;alternatively, acetic acid; alternatively, propionic acid; oralternatively, butyric acid. In an embodiment, the alcohol can be a C₁to C₁₀ alcohol; or alternatively, a C₁ to C₅ alcohol. In someembodiments, the alcohol can be methanol, ethanol, propanol, butanol, orpentanol; alternatively, methanol, ethanol, n-propanol, iso-propanol,n-butanol, or tert-butanol; alternatively, methanol; alternatively,ethanol; alternatively, n-propanol; alternatively, iso-propanol;alternatively, n-butanol; or alternatively, or tert-butanol. In anembodiment, the amine hydrohalide can be a C₁ to C₁₅ hydrohalide. Insome embodiments, the amine hydrohalide may be a methylaminehydrohalide, dimethylamine hydrohalide, trimethylamine hydrohalide,ethylamine hydrohalide, diethylamine hydrohalide, or triethylaminehydrohalide, or triethanolamine hydrochloride; alternatively,methylamine hydrohalide; alternatively, dimethylamine hydrohalide;alternatively, trimethylamine hydrohalide; alternatively, ethylaminehydrohalide; alternatively, diethylamine hydrohalide; alternatively,triethylamine hydrohalide; alternatively, ethanolamine hydrohalide;alternatively, diethanolamine hydrohalide; or alternatively,triethanolamine hydrochloride. In some embodiments, the aminehydrohalide can be an amine hydrochloride, hydrobromide, or hydroiodide;or alternatively, hydrochloride. In some embodiments, the aminehydrohalide can be methylamine hydrochloride, methylamine hydrobromide,dimethylamine hydrochloride, dimethylamine hydrobromide, trimethylaminehydrochloride, trimethylamine hydrobromide, ethylamine hydrochloride,ethylamine hydrobromide, diethylamine hydrochloride, diethylaminehydrobromide, triethylamine hydrochloride, triethylamine hydrobromide,ethanolamine hydrochloride, ethanolamine hydrobromide, diethanolaminehydrochloride, diethanolamine hydrobromide, triethanolaminehydrochloride, triethanolamine hydrobromide; alternatively, methylaminehydrochloride, dimethylamine hydrochloride, trimethylaminehydrochloride, ethylamine hydrochloride, diethylamine hydrochloride,triethylamine hydrochloride, ethanolamine hydrochloride, diethanolaminehydrochloride, or triethanolamine hydrochloride; alternatively,methylamine hydrochloride; alternatively, dimethylamine hydrochloride;alternatively, trimethylamine hydrochloride; alternatively, ethylaminehydrochloride; alternatively, diethylamine hydrochloride; alternatively,triethylamine hydrochloride; alternatively, ethanolamine hydrochloride;alternatively, diethanolamine hydrochloride; or alternatively,triethanolamine hydrochloride.

In an embodiment, the non-metal amidine compound can be utilized withoutfurther isolation or purification. In some embodiments, the non-metalamidine compound can be isolated; alternatively, purified; oralternatively, isolated and purified. In an embodiment, wherein theamidine compound can be prepared in a solvent (aprotic or polaraprotic), the method to prepare the amidine compound can include a stepof isolating the amidine compound by evaporating the solvent. In anembodiment wherein the non-metal amidine compound can be prepared in asolvent (aprotic or polar aprotic), the method to prepare the non-metalamidine compound can include the step of isolating the amidine compoundby filtering the solution to remove particulate materials and/orbyproducts of the reaction and evaporating the solvent. In embodiments,the method to prepare the non-metal amidine compound can include apurification step wherein the non-metal amidine compound can be purifiedby dissolving the non-metal amidine compound in a solvent and filteringthe solution to remove particulate materials and/or byproducts of thereaction. The solvent utilized to purify the non-metal amidine compoundcan be the same solvent utilized to form the non-metal amidine compoundor it may be different than the solvent utilized to form the non-metalamidine compound. In some embodiments, the method to prepare thenon-metal amidine compound may include a purification step wherein thenon-metal amidine compound can be purified by washing with a solvent. Inother embodiments, the method to prepare the non-metal amidine compoundcan include a purification step of recrystallizing the amidine compound.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g., at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

In an aspect the metal amides, which are utilized in the preparation ofsome of the metal amidinates and amidine compound described herein, canbe prepared by a method comprising: a) contacting an amine having an—NH₂ group and a compound capable of abstracting the proton from theamine —NH₂ group; and b) forming the metal amide. Generally, the metalamide can be formed under conditions capable of forming a metal amide.In some embodiments, the metal amide may be isolated; alternatively,purified; or alternatively, isolated and purified.

In an embodiment, the amine may have Structures A1, A2, A3, or A4;alternatively, A1; alternatively, A2; alternatively, A3; oralternatively, A4. Generally, utilizing the present disclosure, one canreadily recognize the metal amine structure and the nitrile structurenecessary to produce a particular metal amidinate. For example, theamine having Structure A1 can utilized when

R¹—NH₂ H₂N—L¹—NH₂ D¹ NH₂)_(q) Q¹—L³—NH₂ Structure A1 Structure A2Structure A3 Structure MA4preparing a metal amidinate having Structure MAM6, MAM8, or MAM10 and/oran amidine compound having Structure AM6, AM8, or AM10, the amine havingStructure A2 is utilized when preparing a metal amidinate havingStructure MAM7 and/or an amidine compound having Structure AM7, theamine having Structure A3 is utilized when preparing a metal amidinatehaving Structure MAM9 and/or an amidine compound having Structure AM9,an the amine having Structure A4 is utilized when preparing a metalamidinate having Structure MAM16. MAM18, or MAM20 and/or an amidinecompound having Structure AM16, AM18, or AM20. However, it should benoted that the methods described herein provide for the conversionamidine compounds having Structures AM6-10, AM16, AM18, and/or AM20(wherein R³ is hydrogen) or metal amidinates having StructuresMAM6-MAM10, MAM16, MAM18, and/or MAM20 (wherein R³ is hydrogen) intoamidine compounds having Structures NP1—NP5, NP11, NP13, and/or NP15(wherein R³ is not hydrogen). R¹, D¹, L¹, L³, Q¹, and q within amineStructures A1-A4 are independently described as features of theN²-phosphinyl amidine compounds Structures NP1—NP10, NP11, NP13, NP15,NP16, NP18, and/or NP20. Since amine Structures A1-A4 are ultimatelyutilized to prepare embodiments of N²-phosphinyl amidine compoundshaving Structures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20,the R¹, D¹, L¹, L³, Q¹, and q, descriptions for the N²-phosphinylamidine compounds may be utilized without limitation to further describethe amine Structures A1-A4 Amines are disclosed herein and may beutilized, without limitation, to further describe the method to preparethe amidine compound.

In an embodiment, the metal compound capable of abstracting the protonfrom an amine having an —NH2 group can be a metal hydride or a metalalkyl. Generally, metal hydrides and metal alkyls capable of abstractingthe proton from an amine having an —NH2 group can be the same as thosecapable of abstracting the proton from the amidine compound (describedherein). Consequently, the metal hydrides and metal alkyls describeherein as capable of capable of abstracting the proton from the amidinecompound can be utilized, without limitation, to further describe themethod preparing the metal amide.

Generally, the amine and the metal compound can be combined in an amineto metal compound equivalent ratio of at least 0.9:1. In an embodiment,the amine and the metal compound can be combined in an amine to metalcompound equivalent ratio of at least 0.95:1; alternatively, of at least0.975:1; or alternatively, of at least 0.99:1. In some embodiments, theamine and the metal compound can be combined in an amine and metalcompound equivalent ratio ranging from 0.9:1 to 1.25:1; alternatively,ranging from 0.95:1 to 1.20:1; alternatively, ranging from 0.975:1 to1.15:1; or alternatively, ranging from 0.99:1 to 1.10:1. In otherembodiments, the amine and the metal compound can be combined in anamine to metal compound equivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming the metal amide caninclude a temperature of at least −45° C.; alternatively, of at least−30° C.; alternatively, of at least −25° C.; or alternatively, of atleast −20° C. In some embodiments, the reaction conditions capable offorming a metal amide can include a temperature ranging from −45° C. to60° C.; alternatively, ranging from −30° C. to 50° C.; alternatively,ranging from −25° C. to 45° C.; or alternatively, ranging from −20° C.to 40° C.

In some embodiments, the conditions capable of forming the metal amidecan include an initial metal compound and amine contact temperature anda second temperature to form the metal amide. It should be noted thewhen the conditions capable of forming the metal amide is described asoccurring at two temperatures (one for the contact of the metal compoundand the amine and one for the formation of the metal amide) that thisdescription does not exclude the prospect that metal amide can be formedat the contact temperature. The description just relates that, in someembodiments, the formation can proceed better when the initial contactbetween the metal compound and amine is performed at one temperature andthe formation of the metal amide is completed at a second differenttemperature.

In an embodiment, the metal compound and amine can be contacted at atemperature ranging from −45° C. to 20° C.; alternatively, ranging from−30° C. to 15° C.; alternatively, ranging from −25° C. to 45° C.; oralternatively, ranging from −20° C. to 40° C. In an embodiment, themetal amide can be formed at a temperature ranging from 0° C. to 20° C.;alternatively, ranging from 5° C. to 15° C.; alternatively, ranging from10° C. to 45° C.; or alternatively, ranging from 15° C. to 40° C.

In an embodiment, the conditions capable of forming the metal amide caninclude a metal amide formation time of at least 5 minutes;alternatively, of at least 10 minutes; alternatively, of at least 15minutes; or alternatively, of at least 20 minutes. In some embodiments,the conditions capable of forming the metal amide can include a metalamide formation time ranging from 5 minutes to 6 hours; alternatively,ranging from 10 minutes to 5 hours; alternatively, ranging from 15minutes to 4.5 hours; or alternatively, ranging from 20 minutes to 4hours.

In an embodiment, the metal compound and the amine can be contacted inan aprotic solvent. In some embodiments, the metal compound and theamine can be contacted in a polar aprotic solvent. Aprotic solventswhich can be utilized include hydrocarbon solvents and ether solvents.Polar aprotic solvents which can be utilized include ether solvents.Solvents are generally disclosed herein and any general or specificaprotic solvent and/or polar aprotic solvent described herein can beutilized to further describe the method of preparing the metal amide bycontacting a metal compound and an amine compound and forming a metalamide.

In an embodiment, the metal amide can be utilized without furtherisolation or purification. In some embodiments, the metal amide can beisolated; alternatively, purified; or alternatively, isolated andpurified. In an embodiment, the method can include a step of isolatingthe metal amide by filtering the metal amide from the solution. In someembodiments, the method can include a step of purifying the metal amideby washing the metal amide with a solvent. Generally, the washingsolvent is an aprotic solvent. In other embodiments, the washing solventcan be polar aprotic solvent. In other embodiments, the washing solventcan be a non-polar aprotic solvent.

Generally, methods of preparing an amidine compound utilizing metalamides and nitriles produce amidine compounds having two N² hydrogens(e.g., amidine compounds having Structure AM6-AM10, AM16, AM18, and/orAM20) which can then be utilized to prepare an N²-phosphinyl amidinecompound having an N² hydrogen atom (e.g. N²-phosphinyl amidinecompounds having Structures NP6 —NP10, NP16, NP18, and/or NP20,respectively) utilizing methods described herein. However, in someinstances it may be desirable to have N²-phosphinyl amidine compoundshaving a non-hydrogen N² group; e.g., N²-phosphinyl amidine compoundshaving Structures NP1—NP5, NP11, NP13, and/or NP15 wherein R³ is anon-hydrogen group. Some methods of preparing the N²-phosphinyl amidinecompounds having a non-hydrogen N² group include: a) alkylating anN²-phosphinyl amidine compound having an N² hydrogen atom (e.g.,N²-phosphinyl amidine compounds having Structure NP6—NP10, NP16, NP18,and/or NP20), b) alkylating a metal amidinate (e.g., an amidinate havingStructure MAM6-MAM10, MAM16, MAM18, and /MAM20) to produce an amidinecompound having Structures AM1-AM5, AM11, AM13, AM15 wherein R³ is annon-hydrogen group and converting the amidine compound to anN²-phosphinyl amidine compound (e.g., N²-phosphinyl amidine compoundshaving Structure NP1—NP5, NP11, NP13, and/or NP15) utilizing methodsdescribed herein, and c) preparing an amidine compound having only oneN² hydrogen atom by contacting an N-substituted α-chloro imine with anamine and converting the amidine compound to an N²-phosphinyl amidinecompound (e.g., N²-phosphinyl amidine compounds having StructureNP1—NP5, NP11, NP13, and/or NP15) utilizing methods described herein.

In an aspect, a method of preparing an N²-phosphinyl amidine compoundcan comprise: a) contacting an N²-phosphinyl amidine compound having anN² hydrogen and a metallic compound capable of abstracting a proton fromthe N²-phosphinyl amidine compound; b) forming a metal N²-phosphinylamidinate; c) contacting a halogenated compound with the formed metalN²-phosphinyl amidinate and d) forming the N²-phosphinyl amidinecompound. Generally, the N²-phosphinyl metal amidinate can be formedunder conditions capable of forming a metal amidinate. In an embodiment,the metal N²-phosphinyl amidinate can be isolated; alternatively,purified; or alternatively, isolated and purified. Generally, theN²-phosphinyl amidine compound can be formed under conditions capable offorming an N²-phosphinyl amidine compound. In an embodiment, theN²-phosphinyl amidine compound can be isolated; alternatively, purified;or alternatively, isolated and purified.

In an embodiment, the amidine compound having an N² hydrogen can haveStructure NP6, NP7, NP8, NP9, NP10, NP16, NP18, or NP20; alternatively,NP6, NP7, NP8, NP9, or NP10; alternatively, NP16, NP18, or NP20;alternatively, NP6 or NP16; alternatively, NP8 or NP18; alternatively,NP10 or NP20; alternatively, NP6; alternatively, NP7; alternatively,NP8; alternatively, NP9; alternatively, NP10; alternatively, NP16;alternatively, NP18; or alternatively, NP20. R¹, R², D¹, D², L¹, L², L³,Q¹, q, and r within amidine compounds having an N² hydrogen havingStructures NP6 —NP10, NP16, NP18, and/or NP20 are independentlydescribed as features of the N²-phosphinyl amidine compound StructuresNP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20. Since N²-phosphinylamidine compound Structures NP6—NP10, NP16, NP18, and/or NP20 areutilized to prepare the N²-phosphinyl amidine compounds havingStructures NP1—NP5, NP11, NP13, and NP15 (respectively), the R¹, R², D¹,D², L¹, L², L³, Q¹, q, and r descriptions for the N²-phosphinyl amidinecompounds having Structures NP1-NP10, NP11, NP13, NP15, NP16, NP18,and/or NP20 can be utilized without limitation to further describe theN²-phosphinyl amidine compounds having Structures NP6—NP10, NP16, NP18,and/or NP20.

In an embodiment, the metal compound capable of abstracting a protonfrom the N²-phosphinyl amidine compound can be a metal hydride or ametal alkyl. Generally, metal hydrides and metal alkyls capable ofabstracting the proton from the N²-phosphinyl amidine compound are thesame as those capable of abstracting the proton from the amidinecompound. Consequently, the metal hydrides and metal alkyls describedherein as capable of abstracting the proton from the amidine compoundcan be utilized, without limitation, to further describe the methodpreparing the N²-phosphinyl amidine compound.

Generally, the N²-phosphinyl amidine compound and the metal compound canbe combined in an amidine to metal compound equivalent ratio of at least0.9:1. In an embodiment, the N²-phosphinyl amidine compound and themetal compound can be combined in an amidine to metal compoundequivalent ratio of at least 0.95:1; alternatively, of at least 0.975:1;or alternatively, of at least 0.99:1. In some embodiments, theN²-phosphinyl amidine compound and the metal compound can be combined inan amidine and metal compound equivalent ratio ranging from 0.9:1 to1.25:1; alternatively, ranging from 0.95:1 to 1.20:1; alternatively,ranging from 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to1.10:1. In other embodiments, the N²-phosphinyl amidine compound and themetal compound can be combined in an amidine to metal compoundequivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming the metalN²-phosphinyl amidinate can include a temperature of at least −45° C.;alternatively, of at least −30° C.; alternatively, of at least −25° C.;or alternatively, of at least −20° C. In some embodiments, the reactionconditions capable of forming a metal N²-phosphinyl amidinate caninclude a temperature ranging from −45° C. to 60° C.; alternatively,ranging from −30° C. to 50° C.; alternatively, ranging from −25° C. to45° C.; or alternatively, ranging from −20° C. to 40° C.

In some embodiments, the conditions capable of forming the metalN²-phosphinyl amidinate can include an initial metal compound andamidine contact temperature and a second temperature to form the metalN²-phosphinyl amidinate. It should be noted that when the conditionscapable of forming the metal N²-phosphinyl amidinate is described asoccurring at two temperatures (one for the contact of the metal compoundand the amidine and one for the formation of the metal N²-phosphinylamidinate) that this description does not exclude the prospect that themetal N²-phosphinyl amidinate can be formed at the contact temperature.The description just relates that, in some embodiments, the formationcan proceed better when the initial contact between the metal compoundand amidine is performed at one temperature and the formation of themetal N²-phosphinyl amidinate is completed at a second differenttemperature.

In an embodiment, the metal compound and amidine can be contacted at atemperature ranging from −45° C. to 20° C.; alternatively, ranging from−30° C. to 15° C.; alternatively, ranging from −25° C. to 45° C.; oralternatively, ranging from −20° C. to 40° C. In an embodiment, themetal N²-phosphinyl amidinate can be formed at a temperature rangingfrom 0° C. to 20° C.; alternatively, ranging from 5° C. to 15° C.;alternatively, ranging from 10° C. to 45° C.; or alternatively, rangingfrom 15° C. to 40° C.

In an embodiment, the conditions capable of forming the metalN²-phosphinyl amidinate can include a metal N²-phosphinyl amidinateformation time of at least 5 minutes; alternatively, of at least 10minutes; alternatively, of at least 15 minutes; or alternatively, of atleast 20 minutes. In some embodiments, the conditions capable of formingthe metal N²-phosphinyl amidinate can include a metal N²-phosphinylamidinate formation time ranging from 5 minutes to 6 hours;alternatively, ranging from 10 minutes to 5 hours; alternatively,ranging from 15 minutes to 4.5 hours; or alternatively, ranging from 20minutes to 4 hours.

In an embodiment, the metal compound and the N²-phosphinyl amidine canbe contacted in an aprotic solvent. In some embodiments, the metalcompound and the N²-phosphinyl amidine can be contacted in a polaraprotic solvent. Aprotic solvents which can be utilized includehydrocarbon solvents and ether solvents. Polar aprotic solvents whichcan be utilized include ether solvents. Solvents are generally disclosedherein and any general or specific aprotic solvent and/or polar aproticsolvent described herein can be utilized to further describe the methodof preparing the metal N²-phosphinyl amidinate by contacting a metalcompound and an N²-phosphinyl amidine compound and forming a metalN²-phosphinyl amidinate.

In an embodiment, the metal N²-phosphinyl amidinate can be utilizedwithout further isolation or purification. In some embodiments, themetal N²-phosphinyl amidinate can be isolated; alternatively, purified;or alternatively, isolated and purified. In an embodiment, the methodcan include a step of isolating the metal N²-phosphinyl amidinate byfiltering the metal N²-phosphinyl amidinate from the solution. In someembodiments, the method can include a step of purifying the metalN²-phosphinyl amidinate by washing the metal N²-phosphinyl amidinatewith a solvent. Generally, the washing solvent is an aprotic solvent. Inother embodiments, the washing solvent can be polar aprotic solvent. Inother embodiments, the washing solvent can be a non-polar aproticsolvent.

In an embodiment, the halogenated compound can have Structure HC1.

X²R³  Structure HC1

X² of Structure HC1 represents a halide. In an embodiment, X² of thehalogenated compound can be fluoride, chloride, bromide, or iodide;alternatively, fluoride; alternatively, chloride; alternatively,bromide; or alternatively, iodide. R³ within halogenated compoundStructure HC1 is independently described as a feature of theN²-phosphinyl amidine compound Structures NP1—NP10, NP11, NP13, NP15,NP16, NP18, and/or NP20. Since halogenated compound HC1 is utilized toprepare embodiments of N²-phosphinyl amidine compounds having StructuresNP1—NP5, NP11, NP13, and/or NP15, the R³ description for theN²-phosphinyl amidine compounds can be utilized without limitation tofurther describe halogenated compounds having Structure HC1. Halogenatedcompounds are disclosed herein and can be utilized, without limitation,to further describe the method to prepare the N²-phosphinyl amidinecompound.

Generally, the halogenated compound and the metal N²-phosphinylamidinate can be combined in a halogenated compound to metalN²-phosphinyl amidate equivalent ratio of at least 0.9:1. In someembodiments, the halogenated compound and the metal N²-phosphinylamidinate can be combined in a halogenated compound to metalN²-phosphinyl amidate equivalent ratio of at least 0.95:1;alternatively, at least 0.975:1; or alternatively, at least 0.99:1. Insome embodiments, the halogenated compound and the metal N²-phosphinylamidinate can be combined in a halogenated compound to metalN²-phosphinyl amidate equivalent ratio ranging from 0.9:1 to 1.25:1;alternatively, ranging from 0.95:1 to 1.20:1; alternatively, rangingfrom 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to 1.10:1.In other embodiments, the halogenated compound and the metalN²-phosphinyl amidinate can be combined in a halogenated compound tometal N²-phosphinyl amidate equivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming an N²-phosphinylamidine compound can include a reaction temperature of at least 0° C.;alternatively, of at least 5° C.; alternatively, of at least 10° C.; oralternatively, of at least 15° C. In some embodiments, the conditionscapable of forming an N²-phosphinyl amidine compound can include areaction temperature ranging from 0° C. to 60° C.; alternatively,ranging from 5° C. to 50° C.; alternatively, ranging from 10° C. to 45°C.; or alternatively, ranging from 15° C. to 40° C. In an embodiment,the conditions capable of forming an N2-phosphinyl amidine compound caninclude a reaction time of at least 5 minutes; alternatively, of atleast 10 minutes; alternatively, of at least 15 minutes; oralternatively, of at least 20 minutes. In some embodiments, theconditions capable of forming an N²-phosphinyl amidine compound caninclude a reaction time ranging from 5 minutes to 6 hours;alternatively, ranging from 10 minutes to 5 hours; alternatively,ranging from 15 minutes to 4.5 hours; or alternatively, ranging from 20minutes to 4 hours.

In an embodiment, the halogenated compound and the metal N²-phosphinylamidinate can be contacted in an aprotic solvent. In some embodiments,the halogenated compound and the metal N²-phosphinyl amidinate can becontacted in a polar aprotic solvent. Aprotic solvents which can beutilized include hydrocarbon solvents and ether solvents. Polar aproticsolvents which can be utilized include ether solvents. Solvents aregenerally disclosed herein and any general or specific aprotic solventand/or polar aprotic solvent described herein can be utilized to furtherdescribe the method of preparing an N²-phosphinyl amidine compoundcomprising contacting a halogenated compound with a metal N²-phosphinylamidinate and forming the N²-phosphinyl amidinate.

In an embodiment, the N²-phosphinyl amidine compound can be utilizedwithout further isolation or purification. In some embodiments, theN²-phosphinyl amidine compound can be isolated; alternatively, purified;or alternatively, isolated and purified. In an embodiment, wherein theN²-phosphinyl amidine compound can be prepared in a solvent (aprotic orpolar aprotic), the method to prepare the N²-phosphinyl amidine compoundcan include a step of isolating the N²-phosphinyl amidine compound byevaporating the solvent. In an embodiment wherein the N²-phosphinylamidine compound can be prepared in a solvent (aprotic or polaraprotic), the method to prepare the N²-phosphinyl amidine compound caninclude the step of isolating the N²-phosphinyl amidine compound byfiltering the solution to remove particulate materials and/or byproductsof the reaction and evaporating the solvent. In embodiments, the methodto prepare the N²-phosphinyl amidine compound can include a purificationstep wherein the N²-phosphinyl amidine compound can purified bydissolving the N²-phosphinyl amidine compound in a solvent and filteringthe solution to remove particulate materials and/or byproducts of thereaction. The solvent utilized to purify the N²-phosphinyl amidinecompound can be the same as the solvent utilized to form theN²-phosphinyl amidine compound or it can be different than the solventutilized to form the N²-phosphinyl amidine compound. In someembodiments, the method to prepare the N²-phosphinyl amidine compoundcan include a purification step of purifying the N²-phosphinyl amidinecompound by washing the N²-phosphinyl amidine compound with a solvent.In other embodiments, the method to prepare the N²-phosphinyl amidinecompound can include a purification step wherein the N²-phosphinylamidine compound is recrystallized.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g., at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

In an aspect, a method of preparing an N²-phosphinyl amidine compoundcan comprise: a) contacting an N²-phosphinyl amidine compound having anN² hydrogen and a metallic compound capable of abstracting the protonfrom the N²-phosphinyl amidine compound; b) forming a metalN²-phosphinyl amidinate; c) contacting a halogenated compound with theformed metal N²-phosphinyl amidinate and d) forming the N²-phosphinylamidine compound. Generally, the metal amidinate can be formed underconditions capable of forming a metal amidinate. In an embodiment, themetal N²-phosphinyl amidinate can be isolated; alternatively, purified;or alternatively, isolated and purified. Generally, the N²-phosphinylamidine compound can be formed under conditions capable of forming anN²-phosphinyl amidine compound. In an embodiment, the N²-phosphinylamidine compound can be isolated; alternatively, purified; oralternatively, isolated and purified.

In an embodiment, the amidine compound having an N² hydrogen can haveStructure NP6, NP7, NP8, NP9, NP10, NP16, NP18 or NP20; alternatively,NP6; alternatively, NP7; alternatively, NP8; alternatively, NP9;alternatively, NP10; alternatively, NP16; alternatively, NP18; oralternatively, NP20. R¹, R², D¹, D², L¹, L², L³, Q¹, q, and r withinamidine compounds having an N² hydrogen having Structures NP6—NP10,NP16, NP18, and NP20 are independently described as features of theN²-phosphinyl amidine compound Structures NP1—NP5. Since N²-phosphinylamidine compound Structures AM1-AM10, AM16, AM18 and AM20 are utilizedto prepare the N²-phosphinyl amidine compounds having StructuresNP1—NP10, NP16, NP18, and NP20 the R¹, R², D¹, D², L¹, L², L³, Q¹, q,and r descriptions for the N²-phosphinyl amidine compounds havingStructures NP1—NP5 can be utilized without limitation to furtherdescribe the N²-phosphinyl amidine compounds having Structures NP6—NP10, NP16, NP18, and NP20 alternatively, Structure NP6; alternatively,Structure NP7; alternatively, Structure NP8; alternatively, NP9;alternatively, Structure NP10; alternatively, Structure NP16;alternatively, Structure NP18; or alternatively, Structure NP20.

In an embodiment, the metal compound capable of abstracting the protonfrom the N²-phosphinyl amidine compound can be a metal hydride or ametal alkyl. Generally, metal hydrides and metal alkyls capable ofabstracting the proton from the N²-phosphinyl amidine compound are thesame as those capable of abstracting the proton from the amidinecompound. Consequently, the metal hydrides and metal alkyls describedherein as capable of abstracting the proton from the amidine compoundcan be utilized, without limitation, to further describe the methodpreparing the N²-phosphinyl amidine compound.

Generally, the N²-phosphinyl amidine compound and the metal compound canbe combined in an amidine to metal compound equivalent ratio of at least0.9:1. In an embodiment, the N²-phosphinyl amidine compound and themetal compound can be combined in an amidine to metal compoundequivalent ratio of at least 0.95:1; alternatively, of at least 0.975:1;or alternatively, of at least 0.99:1. In some embodiments, theN²-phosphinyl amidine compound and the metal compound can be combined inan amidine and metal compound equivalent ratio ranging from 0.9:1 to1.25:1; alternatively, ranging from 0.95:1 to 1.20:1; alternatively,ranging from 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to1.10:1. In other embodiments, the N²-phosphinyl amidine compound and themetal compound can be combined in an amidine to metal compoundequivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming the metalN²-phosphinyl amidinate can include a temperature of at least −45° C.;alternatively, of at least −30° C.; alternatively, of at least −25° C.;or alternatively, of at least −20° C. In some embodiments, the reactionconditions capable of forming a metal N²-phosphinyl amidinate caninclude a temperature ranging from −45° C. to 60° C.; alternatively,ranging from −30° C. to 50° C.; alternatively, ranging from −25° C. to45° C.; or alternatively, ranging from −20° C. to 40° C.

In some embodiments, the conditions capable of forming the metalN²-phosphinyl amidinate can include an initial metal compound andamidine contact temperature and a second temperature to form the metalN²-phosphinyl amidinate. It should be noted the when the conditionscapable of forming the metal N²-phosphinyl amidinate is described asoccurring at two temperatures (one for the contact of the metal compoundand the amidine and one for the formation of the metal N²-phosphinylamidinate) that this description does not exclude the prospect thatmetal N²-phosphinyl amidinate can be formed at the contact temperature.The description just relates that, in some embodiments, the formationproceed better when the initial contact between the metal compound andamidine is performed at one temperature and the formation of the metalN²-phosphinyl amidinate is completed at a second different temperature.

In an embodiment, the metal compound and amidine can be contacted at atemperature ranging from −45° C. to 20° C.; alternatively, ranging from−30° C. to 15° C.; alternatively, ranging from −25° C. to 45° C.; oralternatively, ranging from −20° C. to 40° C. In an embodiment, metalN2-phosphinyl amidinate is formed at a temperature ranging from 0° C. to20° C.; alternatively, ranging from 5° C. to 15° C.; alternatively,ranging from 10° C. to 45° C.; or alternatively, ranging from 15° C. to40° C.

In an embodiment, the conditions capable of forming the metalN²-phosphinyl amidinate can include a metal N²-phosphinyl amidinateformation time of at least 5 minutes; alternatively, of at least 10minutes; alternatively, of at least 15 minutes; or alternatively, of atleast 20 minutes. In some embodiments, the conditions capable of formingthe metal N²-phosphinyl amidinate can include a metal N²-phosphinylamidinate formation time ranging from 5 minutes to 6 hours;alternatively, ranging from 10 minutes to 5 hours; alternatively,ranging from 15 minutes to 4.5 hours; or alternatively, ranging from 20minutes to 4 hours.

In an embodiment, the metal compound and the N²-phosphinyl amidine canbe contacted in an aprotic solvent. In some embodiments, the metalcompound and the N²-phosphinyl amidine can be contacted in a polaraprotic solvent. Aprotic solvents which may be utilized includehydrocarbon solvents and ether solvents. Polar aprotic solvents whichmay be utilized include ether solvents. Solvents are generally disclosedherein and any general or specific aprotic solvent and/or polar aproticsolvent described herein can be utilized to further describe the methodof preparing the metal N²-phosphinyl amidinate by contacting a metalcompound and an N²-phosphinyl amidine compound and forming a metalN²-phosphinyl amidinate.

In an embodiment, the metal N²-phosphinyl amidinate can be utilizedwithout further isolation or purification. In some embodiments, themetal N²-phosphinyl amidinate can be isolated; alternatively, purified;or alternatively, isolated and purified. In an embodiment, the methodcan include a step of isolating the metal N²-phosphinyl amidinate byfiltering the metal N²-phosphinyl amidinate from the solution. In someembodiments, the method can include a step of purifying the metalN²-phosphinyl amidinate by washing the metal N²-phosphinyl amidinatewith a solvent. Generally, the washing solvent is an aprotic solvent. Inother embodiments, the washing solvent can be polar aprotic solvent. Inother embodiments, the washing solvent can be a non-polar aproticsolvent.

In an embodiment, the halogenated compound can have Structure HC1.

X²R³  Structure HC1

X² of Structure HC1 represents a halide. In an embodiment, X² of thehalogenated compound can be fluoride, chloride, bromide, or iodide;alternatively, fluoride; alternatively, chloride; alternatively,bromide; or alternatively, iodide. R³ within halogenated compoundStructure HC1 is independently described as a feature of theN²-phosphinyl amidine compound Structures NP1—NP5. Since halogenatedcompound HC1 is utilized to prepare embodiments of N²-phosphinyl amidinecompounds having Structures NP1—NP5, the R³ description for theN²-phosphinyl amidine compounds can be utilized without limitation tofurther describe the halogenated compound having Structure HC1.Halogenated compounds are disclosed herein and can be utilized, withoutlimitation, to further describe the method to prepare the N²-phosphinylamidine compound.

Generally, the halogenated compound and the metal N²-phosphinylamidinate can be combined in a halogenated compound to metalN²-phosphinyl amidate equivalent ratio of at least 0.9:1. In someembodiments, the halogenated compound and the metal N²-phosphinylamidinate can be combined in a halogenated compound to metalN²-phosphinyl amidate equivalent ratio of at least 0.95:1;alternatively, of at least 0.975:1; or alternatively, of at least0.99:1. In some embodiments, the halogenated compound and the metalN²-phosphinyl amidinate can be combined in a halogenated compound tometal N²-phosphinyl amidate equivalent ratio ranging from 0.9:1 to1.25:1; alternatively, ranging from 0.95:1 to 1.20:1; alternatively,ranging from 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to1.10:1. In other embodiments, the halogenated compound and the metalN²-phosphinyl amidinate can be combined in a halogenated compound tometal N²-phosphinyl amidate equivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming an N²-phosphinylamidine compound can include a reaction temperature of at least 0° C.;alternatively, of at least 5° C.; alternatively, of at least 10° C.; oralternatively, of at least 15° C. In some embodiments, the conditionscapable of forming an N²-phosphinyl amidine compound can include areaction temperature ranging from 0° C. to 60° C.; alternatively,ranging from 5° C. to 50° C.; alternatively, ranging from 10° C. to 45°C.; or alternatively, ranging from 15° C. to 40° C. In an embodiment,the conditions capable of forming an N²-phosphinyl amidine compound caninclude a reaction time of at least 5 minutes; alternatively, of atleast 10 minutes; alternatively, of at least 15 minutes; oralternatively, of at least 20 minutes. In some embodiments, theconditions capable of forming an N²-phosphinyl amidine compound caninclude a reaction time ranging from 5 minutes to 6 hours;alternatively, ranging from 10 minutes to 5 hours; alternatively,ranging from 15 minutes to 4.5 hours; or alternatively, ranging from 20minutes to 4 hours.

In an embodiment, the halogenated compound and the metal N²-phosphinylamidinate can be contacted in an aprotic solvent. In some embodiments,the halogenated compound and the metal N²-phosphinyl amidinate can becontacted in a polar aprotic solvent. Aprotic solvents which can beutilized include hydrocarbon solvents and ether solvents. Polar aproticsolvents which can be utilized include ether solvents. Solvents aregenerally disclosed herein and any general or specific aprotic solventand/or polar aprotic solvent described herein can be utilized to furtherdescribe the method of preparing an N²-phosphinyl amidine compoundcomprising contacting a halogenated compound with a metal N²-phosphinylamidinate and forming the N²-phosphinyl amidinate.

In an embodiment, the N²-phosphinyl amidine compound can be utilizedwithout further isolation or purification. In some embodiments, theN²-phosphinyl amidine compound can be isolated; alternatively, purified;or alternatively, isolated and purified. In an embodiment, wherein theN²-phosphinyl amidine compound is prepared in a solvent (aprotic orpolar aprotic), the method to prepare the N²-phosphinyl amidine compoundcan include a step of isolating the N²-phosphinyl amidine compound byevaporating the solvent. In an embodiment wherein the N²-phosphinylamidine compound is prepared in a solvent (aprotic or polar aprotic),the method to prepare the N²-phosphinyl amidine compound can include thestep of isolating the N²-phosphinyl amidine compound by filtering thesolution to remove particulate materials and/or byproducts of thereaction and evaporating the solvent. In embodiments, the method toprepare the N²-phosphinyl amidine compound can include a purificationstep wherein the N²-phosphinyl amidine compound is purified bydissolving the N²-phosphinyl amidine compound in a solvent and filteringthe solution to remove particulate materials and/or byproducts of thereaction. The solvent utilized to purify the N²-phosphinyl amidinecompound can be the same a solvent utilized to form the N²-phosphinylamidine compound or it can be different than the solvent utilized toform the N²-phosphinyl amidine compound. In some embodiments, the methodto prepare the N²-phosphinyl amidine compound can include a purificationstep of purifying the N²-phosphinyl amidine compound by washing theN²-phosphinyl amidine compound with a solvent. In other embodiments, themethod to prepare the N²-phosphinyl amidine compound can include apurification step wherein the N²-phosphinyl amidine compound isrecrystallized.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g. at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

In an aspect, a method to prepare an amidine compound having only one N²hydrogen atom can comprise: a) contacting a metal amidinate and ahalogenated compound; and b) forming the amidine compound having onlyone N² hydrogen atom. Methods of preparing a metal amidinate aredisclosed herein and can be utilized, without limitation to furtherdescribe the method to prepare an amidine compound having only one N²hydrogen atom. Generally, an amidine compound having only one N²hydrogen atom can be formed under conditions capable of forming anamidine compound having only one N² hydrogen atom. In an embodiment, theamidine compound having only one N² hydrogen atom can be isolated;alternatively, purified; or alternatively, isolated and purified.

In an embodiment, the metal amidinate can have Structure MAM6, MAM7,MAM8, MAM9, MAM10; MAM16; MAM18, or MAM20; alternatively, MAM6;alternatively, MAM7; alternatively, MAM8; alternatively, MAM9;alternatively, MAM10; alternatively, MAM16; alternatively, MAM18 oralternatively, MAM20. R¹, R², D¹, D², L¹, L², L³, Q¹, q, and r withinmetal amidine Structures MAM6-MAM10, MAM16, MAM18 and MAM20 areindependently described as features of the N²-phosphinyl amidinecompound Structures NP1—NP5. Since metal amidine Structures MAM6-MAM10MAM16, MAM18, and MAM20 are utilized to prepare embodiments ofN²-phosphinyl amidine compounds having Structures NP6—NP10, NP16 andNP18, the R¹, R², D¹, D², L¹, L², L³, Q¹, q, and r descriptions for theN²-phosphinyl amidine compounds can be utilized without limitation tofurther describe metal amidine Structures MAM6-MAM10, MAM16, MAM18, andMAM20.

The halogenated compound has been described herein as a component forreacting with an N²-phosphinyl amidinate. Generally, the halogenatedcompounds useful for reacting with an N²-phosphinyl amidinate are thesame as those which can be utilized for reacting with a metal amidinate.Consequently, the halogenated compounds describe herein as a potentialreactant with an N²-phosphinyl amidinate can be utilized, withoutlimitation, to further describe halogenated compound which can becontacted with the metal amidinate.

Generally, the halogenated compound and the metal amidinate can becombined in a halogenated compound to metal amidate equivalent ratio ofat least 0.9:1. In some embodiments, the halogenated compound and themetal amidinate can be combined in a halogenated compound to metalamidate equivalent ratio of at least 0.95:1; alternatively, of at least0.975:1; or alternatively, of at least 0.99:1. In some embodiments, thehalogenated compound and the metal amidinate can be combined in ahalogenated compound to metal amidate equivalent ratio ranging from0.9:1 to 1.25:1; alternatively, ranging from 0.95:1 to 1.20:1;alternatively, ranging from 0.975:1 to 1.15:1; or alternatively, rangingfrom 0.99:1 to 1.10:1. In other embodiments, the halogenated compoundand the metal amidinate can be combined in a halogenated compound tometal N²-phosphinyl amidate equivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming the amidine compoundhaving only one N² hydrogen atom can include a reaction temperature ofat least 0° C.; alternatively, of at least 5° C.; alternatively, of atleast 10° C.; or alternatively, of at least 15° C. In some embodiments,the conditions capable of forming the amidine compound having only oneN² hydrogen atom can include a reaction temperature ranging from 0° C.to 60° C.; alternatively, ranging from 5° C. to 50° C.; alternatively,ranging from 10° C. to 45° C.; or alternatively, ranging from 15° C. to40° C. In an embodiment, the conditions capable of forming the amidinecompound having only one N² hydrogen atom can include a reaction time ofat least 5 minutes; alternatively, of at least 10 minutes;alternatively, of at least 15 minutes; or alternatively, of at least 20minutes. In some embodiments, the conditions capable of forming theamidine compound having only one N² hydrogen atom can include a reactiontime ranging from 5 minutes to 6 hours; alternatively, ranging from 10minutes to 5 hours; alternatively, ranging from 15 minutes to 4.5 hours;or alternatively, ranging from 20 minutes to 4 hours.

In an embodiment, the halogenated compound and the metal amidinate canbe contacted in an aprotic solvent. In some embodiments, the halogenatedcompound and the metal amidinate can be contacted in a polar aproticsolvent. Aprotic solvents which can be utilized include hydrocarbonsolvents and ether solvents. Polar aprotic solvents which can beutilized include ether solvents. Solvents are generally disclosed hereinand any general or specific aprotic solvent and/or polar aprotic solventdescribed herein can be utilized to further describe the method ofpreparing the amidine compound having only one N² hydrogen atomcomprising contacting a halogenated compound with a metal amidinate andforming the amidine compound having only one N² hydrogen atom.

In an embodiment, the amidine compound having only one N² hydrogen atomcan be utilized without further isolation or purification. In someembodiments, the amidine compound having only one N² hydrogen atom canbe isolated; or alternatively, isolated and purified. In an embodiment,wherein the amidine compound having only one N² hydrogen atom can beprepared in a solvent (aprotic or polar aprotic), the method to preparethe N²-phosphinyl amidine compound can include a step of isolating theamidine compound having only one N² hydrogen atom by evaporating thesolvent. In an embodiment wherein the amidine compound having only oneN² hydrogen atom can be prepared in a solvent (aprotic or polaraprotic), the method to prepare the amidine compound having only one N²hydrogen atom can include the step of isolating the amidine compoundhaving only one N² hydrogen atom by filtering the solution to removeparticulate materials and/or byproducts of the reaction and evaporatingthe solvent. In some embodiments, the method to prepare the amidinecompound having only one N² hydrogen atom can include a purificationstep wherein the amidine compound having only one N² hydrogen atom canbe purified by dissolving the amidine compound having only one N²hydrogen atom in a solvent and filtering the solution to removeparticulate materials and/or byproducts of the reaction. The solventutilized to purify the amidine compound having only one N² hydrogen atomcan be the same as the solvent utilized to form the N²-phosphinylamidine compound or it can be different than the solvent utilized toform the amidine compound having only one N² hydrogen atom. In someembodiments, the method to prepare the amidine compound having only onehydrogen atom can include a step of purifying the amidine compoundhaving only one hydrogen atom by washing the amidine compound havingonly one hydrogen atom with a solvent. In other embodiments, the methodto prepare the amidine compound having only one hydrogen atom caninclude a step of purifying the amidine compound having only onehydrogen atom by recrystallization.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g. at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

Generally, the methods for forming the metal amide, the amidinecompound, the metal amidinate, and the N²-phosphinyl amidine compoundcan combined in various embodiments to provide a method of forming anN²-phosphinyl amidine compound having only one N² hydrogen atomutilizing amines, nitriles, compounds capable of abstracting a protonfrom the —NH₂ group, alkylating compounds, and phosphine halides. In anon-limiting embodiment, the method of preparing an N²-phosphinylamidine compound can comprise, or consist essentially of, or consist of:a) contacting the metal amide and a nitrile; b) forming a first metalamidinate; c) contacting the first metal amidinate with a halogenatedcompound; d) forming an amidine compound having only one N² hydrogenatom; e) isolating the amidine compound having only one N² hydrogenatom; f) contacting the amidine compound having only one N² hydrogenatom with a compound capable of abstracting a proton from the amidinecompound having only one N² hydrogen atom; g) forming a second metalamidinate; j) contacting the second metal amidinate and a phosphinehalide; and h) forming the N²-phosphinyl amidine compound. In anembodiment, the metal amidinate formed in step b) is contacted with thehalogenated compound without forming a non-metal amidine compound. Inother embodiments, the first metal amidinate formed in step b) isneutralized with a protic compound to form a non-metal amidine compoundwhich can then be isolated and optionally purified and then utilized toreform the first amidinate by contacting the non-metal amidine compoundwith a metal alkyl. In a further non-limiting embodiment, the method ofpreparing an N²-phosphinyl amidine compound can comprise: a) contactingan amine having a —NH₂ group and a compound capable of abstracting aproton from the —NH₂ group; b) forming a metal amide; c) contacting themetal amide and a nitrile; d) forming a first metal amidinate; e)contacting the first metal amidinate with a halogenated compound; f)forming an amidine compound having only one N² hydrogen atom; g)isolating the amidine compound having only one N² hydrogen atom; h)contacting the amidine compound having only one N² hydrogen atom with acompound capable of abstracting a proton from the amidine compoundhaving only one N² hydrogen atom; i) forming a second metal amidinate;j) contacting the second metal amidinate and a phosphine halide; and k)forming the N²-phosphinyl amidine compound. In an embodiment, the metalamidinate formed in step d) is contacted with the halogenated compoundwithout forming a non-metal amidine compound. In other embodiments, thefirst metal amidinate formed in step d) is neutralized with a proticcompound to form a non-metal amidine compound which can then be isolatedand optionally purified and then utilized to reform the first amidinateby contacting the non-metal amidine compound with a metal alkyl. Thesemethods can contain steps other than those recited in the methods ofpreparing metal amides described herein, methods of preparing metalamidinates described herein, methods of preparing amidine compoundsdescribed herein, methods of alkylating amidine compound (or metalamidinates) described herein, and methods of preparing N²-phosphinylamidine compounds described herein which can be utilized to furtherdescribe these methods. Additional features of each of these steps (e.g.reagent ratios, formation conditions, among other considerations) aredescribed herein and can be utilized to further describe the methods.

Generally, the methods for forming the metal amide, the amidinecompound, the metal amidinate, and the N²-phosphinyl amidine compoundcan combined in various methods to provide a method to form anN²-phosphinyl amidine compound utilizing amines, nitriles, compoundscapable of abstracting a proton from the —NH₂ group, and phosphinehalides. In a non-limiting embodiment, a method of preparing anN²-phosphinyl amidine compound can comprise a) contacting a metal amideand a nitrile; b) forming a metal amidinate; c) contacting the metalamidinate (formed in step b) and a phosphine halide; and d) forming theN²-phosphinyl amidine compound. In an embodiment, the metal amidinateformed in step b) is contacted with the phosphine halide without forminga non-metal amidine compound. In another exemplary embodiment, a methodof preparing an N²-phosphinyl amidine compound can comprise a)contacting an amine having a —NH₂ group and a compound capable ofabstracting a proton from the —NH₂ group; b) forming a metal amide; c)contacting the metal amide and a nitrile; d) forming a metal amidinate;e) contacting the metal amidinate (formed in step d) and a phosphinehalide; and f) forming the N²-phosphinyl amidine compound. In anembodiment, the metal amidinate formed in step d) is contacted with thephosphine halide without forming a non-metal amidine compound.

In another non-limiting embodiment, a method of preparing anN²-phosphinyl amidine compound can comprise: a) contacting a metal amideand a nitrile; b) forming a first metal amidinate; c) neutralizing thefirst metal amidinate with a protic compound to form an amidine compoundhaving an N² hydrogen atom; d) contacting the amidine compound having anN² hydrogen atom with a metallic compound capable of abstracting thehydrogen atom from the amidine compound; e) forming a second metalamidinate; f) contacting the second metal amidinate and a phosphinehalide; and f) forming the N²-phosphinyl amidine compound. In a furtherembodiment, a method of preparing an N²-phosphinyl amidine compound cancomprise: a) contacting an amine having a —NH₂ group and a compoundcapable of abstracting a proton from the —NH₂ group; b) forming a metalamide; c) contacting the metal amide and a nitrile; d) forming a firstmetal amidinate; e) neutralizing the first metal amidinate with a proticcompound to form an amidine compound having an N² hydrogen atom; f)contacting the amidine compound having an N² hydrogen atom with ametallic compound capable of abstracting the hydrogen atom from theamidine compound; g) forming a second metal amidinate; h) contacting thesecond metal amidinate and a phosphine halide; and i) forming theN²-phosphinyl amidine compound. These methods can contain steps otherthan those recited in the methods of preparing metal amides describedherein, methods of preparing metal amidinates described herein, methodsof preparing amidine compounds described herein, and methods ofpreparing N²-phosphinyl amidine compounds described herein and can beutilized to further describe these methods. Additional features of eachof these steps (e.g. reagent ratios, formation conditions, among otherconsiderations) are described herein and can be utilized to furtherdescribe the methods.

In an embodiment, step a) can comprise contacting an amine having a —NH₂group and a compound capable of abstracting a proton from the —NH₂ groupand forming a metal amide. In an embodiment, the compound capable ofabstracting a proton from the —NH₂ group can be a metal alkyl. In someembodiments, the compound capable of abstracting a proton from the —NH₂group can be an alkyl lithium and the metal amide formed is a lithiumamide. Metal alkyl and alkyl lithium compounds are independentlydisclosed herein and can be utilized without limitation to furtherdescribe the methods. In an embodiment, the step of contacting a metalamide and a nitrile can also be a step of contacting a metal amide and anitrile under conditions suitable to form a metal amidinate. It shouldbe appreciated that other methods of preparing N²-phosphinyl amidinecompounds can be provided using the steps described herein and thatthese steps can be carried out in any order compatible with one or moreuser and/or process desired goals. In an embodiment, the method ofpreparing an N²-phosphinyl amidine compound is carried out in the orderdescribed herein. For example, the method of preparing an N²-phosphinylamidine compound can comprise formation of a metal amide by contactingof an amine group and a first metal alkyl under conditions suitable forthe formation of a metal amide. The metal amide can subsequently becontacted with a nitrile to form an intermediate which can be quenchedby contacting the intermediate with a proton source to form a quenchedintermediate. The quenched intermediate can be isolated; alternatively,purified; or alternatively, isolated and purified. The isolated and/orpurified intermediate can be reacted with second metal alkyl to producea metal amidinate which is subsequently contacted with a phosphinehalide under conditions suitable for the formation of an N²-phosphinylamidine compound. In an embodiment, the first metal alkyl and the secondmetal alkyl can be the same. In an embodiment, the first metal alkyl andthe second metal alkyl can be different.

In an embodiment, the method of preparing an N²-phosphinyl amidinecompound can comprise formation of a metal amide by contacting of anamine group and a metal alkyl under conditions suitable for theformation of a metal amide. The metal amide can subsequently becontacted with a nitrile to form an intermediate which can subsequentlycontacted with a phosphine halide under conditions suitable for theformation of an N²-phosphinyl amidine compound. In such embodiments,formation of the N²-phosphinyl amidine compound can occur in the absenceof a quenched intermediate. In such embodiments, formation of theN²-phosphinyl amidine compound can occur in the absence of a secondmetal alkyl. Other embodiments of preparing the amidine compoundsutilizing steps of this disclosure will be apparent to those of ordinaryskill in the art by reading the present disclosure.

In an embodiment, the method of preparing an amidine compound havingonly one N² hydrogen atom can comprise: a) contacting a first amine andan acid halide; b) forming an amide; c) contacting the amide withphosphorus pentachloride; d) forming an N-substituted α-chloro imine; e)contacting the N-substituted α-chloro imine with a second amine; and f)forming the amidine compound having only one N² hydrogen atom. In anembodiment, the amide can be formed under conditions capable of formingan amide. In some embodiments, the amide can be isolated; alternatively,purified; alternatively, isolated and purified. In an embodiment, theN-substituted α-chloro imine can be formed under conditions capable offorming an N-substituted α-chloro imine. In an embodiment, theN-substituted α-chloro imine can be isolated; alternatively, purified;or alternatively, isolated and purified. In an embodiment, the amidinecompound having only one N² hydrogen atom can be isolated;alternatively, purified; or alternatively, isolated and purified. In anembodiment, the amidine compound having only one N² hydrogen atom can beformed under conditions capable of forming an amidine compound havingonly one N² hydrogen atom.

In an embodiment, the first amine can have Structure A1, A2, A3, or A4;alternatively, Structure A1; alternatively, Structure A2; alternatively,A3; or alternatively, Structure A4. Generally, utilizing the presentdisclosure, one can readily recognize the amine structure necessary toproduce a particular amidine compound or N²-phosphinyl amidine compound.For example, the amine having Structure A1 can be utilized whenpreparing an amidine compound having Structure AM1, AM3, or AM5 and/oran N²-phosphinyl amidine compound having Structure NP1, NP3, or NP5, theamine having Structure A2 can be utilized when preparing an amidinecompound having Structure AM2 and/or an N²-phosphinyl amidine compoundhaving Structure NP2, the amine having Structure A3 can utilized whenpreparing an amidine compound having Structure AM4 and/or anN²-phosphinyl amidine compound having Structure AM4, the amine havingStructure A4 can be utilized when preparing an amidine compound havingStructure AM11, AM13, or AM15 and/or an N²-phosphinyl amidine compoundhaving Structure NP11, NP13, or NP15 Amines having Structure A1, A2, A3,and A4 are describe herein and can be utilized without limitation tofurther describe the method of preparing an amidine compound having onlyone N² hydrogen atom.

In an embodiment, the acid halide can have Structure AC1, AC2, or AC3;alternatively, AC1; alternatively, AC2; or alternatively, AC3.Generally, utilizing the present disclosure, one can readily recognizethe acid halide structure necessary to produce a particular amidinecompound or N²-phosphinyl amidine compound. For example, the acid halidehaving Structure AC1 can be

utilized when preparing an amidine compound having Structure AM1, AM2,AM4, AM11, AM12, or AM14 and/or an N²-phosphinyl amidine compound havingStructure NP1, NP2, NP4, NP11, NP12, or NP12, the acid halide havingStructure AC2 can be utilized when preparing an amidine having StructureAM3 or AM13 and/or an N²-phosphinyl amidine compound having StructureNP3, or NP13, and the acid halide having Structure AC3 can be utilizedwhen preparing an amidine compound having Structure AM5 or AM15 and/oran N²-phosphinyl amidine compound having Structure NP5 or NP15. R², D²,L², and q within acid halide Structures AC1-AC3 are independentlydescribed as features of the N²-phosphinyl amidine compound havingStructures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and NP20. Since acidhalide Structures AC1-AC3 are utilized to prepare embodiments ofN²-phosphinyl amidine compounds having Structures NP1—NP5, NP11, NP13,and NP15, the R², D², L², and q descriptions for the N²-phosphinylamidine compounds can be utilized without limitation to further describeacid halide Structures AC1-AC3. In an embodiment, X³ of acid halideStructures AC1-AC3 represents a halide. In an embodiment, X³ of the acidhalide can be fluoride, chloride, bromide, or iodide; alternatively,fluoride; alternatively, chloride; alternatively, bromide; oralternatively, iodide.

In an embodiment, the formed amide can have Structure AD1, AD2, AD3,AD4, or AD5; alternatively, AD1; alternatively, AD2; alternatively, AD3;alternatively, AD4; or alternatively, AD5.

Generally, utilizing the present disclosure, one can readily recognizethe acid halide structure necessary to produce a particular amide. Forexample, the acid halide having Structure AC1 can be utilized whenpreparing the amide having Structure AD1, AD2, AD4, or AD11, the acidhalide having Structure AC2 can be utilized when preparing the amidehaving Structure AD3 or AD13, and the acid halide having Structure AC3can be utilized when preparing an amidine compound having Structure AD5or AD15. Generally utilizing the present disclosure, one can readilyrecognize the amine structure necessary to produce a particular amide.For example, the amine having Structure A1 can be utilized whenpreparing the amide having Structure AD1, AD3, or AD5, the amine havingStructure A2 can be utilized when preparing the amide having StructureAD2, the amine having Structure A3 can be utilized when preparing theamide having Structure AD4, and the amine having Structure A4 can beutilized when preparing the amide having Structure AD11, AD13, or AD15.R¹, R², D¹, D², L¹, L², L³, Q¹, q, and r within amide StructuresAD1-AD5, AD11, AD13, and/or AD15 are independently described as featuresof the N²-phosphinyl amidine compound Structures NP1—NP10, NP11, NP13,NP15, NP16, NP18, and/or NP20. Since the amide having StructuresAD1-AD5, AD11, AD13, and/or AD15 are utilized to prepare embodiments ofN²-phosphinyl amidine compounds having Structures NP1—NP10, NP11, NP13,NP15, NP16, NP18, and/or NP20, the R¹, R², D¹, D², L¹, L², L³, Q¹, q,and r descriptions for the N²-phosphinyl amidine compounds can beutilized without limitation to further describe the amide havingStructures AD1-AD5, AD11, AD13, and/or AD15.

Generally, the acid halide and the first amine can be combined in anacid halide to first amine equivalent ratio of at least 0.9:1. In someembodiments, the acid halide and the first amine can be combined in anacid halide to first amine equivalent ratio of at least 0.95:1;alternatively, of at least 0.975:1; or alternatively, of at least0.99:1. In some embodiments, the acid halide and the first amine can becombined in an acid halide to first amine equivalent ratio ranging from0.9:1 to 1.25:1; alternatively, ranging from 0.95:1 to 1.20:1;alternatively, ranging from 0.975:1 to 1.15:1; or alternatively, rangingfrom 0.99:1 to 1.10:1. In other embodiments, the acid halide and thefirst amine can be combined in an acid halide to first amine equivalentratio of about 1:1.

In some embodiments, the step of contacting the first amine and the acidhalide further comprises contacting the first amine and the acid halidewith a compound capable of forming a hydrogen halide salt (i.e. can be astep of contacting a first amine, an acid halide, and a compound capableof forming a hydrogen halide salt). In an embodiment, the compoundcapable of forming a hydrogen halide salt is an amine. In someembodiments, the amine utilized to form a hydrogen halide salt can havethe formula (R^(A))₃N. In an embodiment, each R^(A) independently can bea C₁ to C₁₀ hydrocarbyl group; alternatively, a C₁ to C₅ hydrocarbylgroup; alternatively, a C₁ to C₁₀ alkyl group; or alternatively, a C₁ toC₅ alkyl group. Hydrocarbyl and alkyl groups are independently describedherein (for example as substitutent groups for substituent R¹ groups,among other places) and can be utilized without limitation to furtherdescribe the amine having the formula (R^(A))₃N. In some embodiments,the amine utilized as the compound capable of forming a hydrogen halidesalt can be trimethylamine or triethylamine; alternatively,trimethylamine; or alternatively, triethylamine.

Generally, the compound capable of forming a hydrogen halide salt, whenused, can be utilized at a compound capable of forming a hydrogen halidesalt to first amine equivalent ratio of at least 1:1. In an embodiment,the compound capable of forming a hydrogen halide salt, when used, canbe utilized at a compound capable of forming a hydrogen halide salt tofirst amine equivalent ratio of at least 1.0251; alternatively, of atleast 1.05:1; or alternatively, of at least 1.075:1. In someembodiments, the compound capable of forming a hydrogen halide salt,when used, can be utilized at a compound capable of forming a hydrogenhalide salt to first amine equivalent ratio ranging from 1:1 to 2:1;alternatively, ranging from 1.025:1 to 1.50:1; alternatively, rangingfrom 1.05:1 to 1.5:1; or alternatively, ranging from 1.075:1 to 1.25:1.

In an embodiment, the conditions capable of forming the metal amidinatecan include a temperature of at least −25° C.; alternatively, of atleast −20° C.; alternatively, of at least −25° C.; or alternatively, ofat least −10° C. In some embodiments, the reaction conditions capable offorming a metal amidinate can include a temperature ranging from −25° C.to 100° C.; alternatively, ranging from −20° C. to 90° C.;alternatively, ranging from −15° C. to 85° C.; or alternatively, rangingfrom −10° C. to 80° C.

In some embodiments, the conditions capable of forming the amide caninclude an initial first amine and acid halide contact temperature and asecond temperature to form the amide. It should be noted the when theconditions capable of forming the amide is described as occurring at twotemperatures (one for the contact of the first amine and the acid halideand one for the formation of the amide) that this description does notexclude the prospect that the amide may be formed at the contacttemperature. The description just relates that, in some embodiments, theformation may proceed better when the initial contact between the firstamine and acid halide is performed at one temperature and the formationof the amide is completed at a second different temperature.

In an embodiment, the first amine and acid halide can be contacted at atemperature ranging from −25° C. to 40° C.; alternatively, ranging from−20° C. to 35° C.; alternatively, ranging from −15° C. to 30° C.; oralternatively, ranging from −10° C. to 25° C. In an embodiment, theamide can be formed at a temperature ranging from 10° C. to 100° C.;alternatively, ranging from 15° C. to 90° C.; alternatively, rangingfrom 20° C. to 85° C.; or alternatively, ranging from 25° C. to 80° C.In an embodiment, the conditions capable of forming the amide caninclude a reaction time of at least 15 minutes; alternatively, of atleast 30 minutes; alternatively, of at least 45 minutes; oralternatively, of at least 1 hour. In some embodiments, the conditionscapable of forming the amide can include a reaction time ranging from 15minutes to 36 hours; alternatively, ranging from 30 minutes to 30 hours;alternatively, ranging from 45 minutes to 24 hours; or alternatively,ranging from 1 hour to 18 hours.

In an embodiment, the first amine and the acid halide can be contactedin an aprotic solvent. In some embodiments, the first amine and the acidhalide can be contacted in a polar aprotic solvent. Aprotic solventswhich can be utilized include hydrocarbon, halogenated hydrocarbonsolvents, and ether solvents. Solvents are generally disclosed hereinand any general or specific aprotic solvent and/or polar aprotic solventdescribed herein can be utilized to further describe the method ofpreparing an amide.

In an embodiment, the amide can be utilized without further isolation orpurification. In some embodiments, the amide can be isolated;alternatively, purified; or alternatively, isolated and purified. In anembodiment, the method can include a step of isolating the amide byevaporating the solvent in which the amide is formed, treating the amidewith water, and separating the amide by filtration. In some embodiments,the method can include a step of isolating the amide by contacting thecomposition comprising the amide and the solvent in which the amide wasformed with water, separating the aqueous portion from the solvent inwhich the amide was formed, and evaporating the solvent in which theamide was formed. In embodiments, the method to prepare the amide caninclude a purification step wherein the amide is purified by dissolvingthe amide in a solvent and filtering the solution to remove particulatematerials and/or byproducts of the reaction. The solvent utilized topurify the amide can be the same as the solvent utilized to form theamide or it can be different than the solvent utilized to form amide. Insome embodiments, the method can include a purification step wherein theamide is purified by washing the amide with a solvent. In otherembodiments, the method to prepare the amide can include a purificationstep wherein the amide is recrystallized.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g. at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

In some embodiments, the N-substituted α-chloro imine can have StructureCI1, CI2, CI3, CI4, CI5, CI11, CI13, or CI5; alternatively, StructureCI1, CI2, CI3, CI4, or CI5; alternatively, Structure CI11, CI13, or CI5;alternatively, Structure CI1 or CI11; alternatively, Structure CI3 orCI13; alternatively, Structure CI5 or CI15; alternatively, StructureCI1; alternatively, Structure CI2; alternatively, Structure CI3;alternatively, Structure CI4; alternatively, CI5; alternatively,Structure CI11; alternatively, Structure CI13; or alternatively,Structure C15.

Generally, utilizing the present disclosure, one can readily recognizethe amide structure necessary to produce a particular α-chloro imine.For example, the amide having Structure AD1 can be utilized whenpreparing an N-substituted α-chloro imine having Structure CI1, theamide having Structure AD2 can be utilized when preparing anN-substituted α-chloro imine having Structure CI2, the amide havingStructure AD3 can be utilized when preparing an N-substituted α-chloroimine having Structure CI3, the amide having Structure AD4 can beutilized when preparing an N-substituted α-chloro imine having StructureCI4, the amide having Structure AD5 can be utilized when preparing anN-substituted α-chloro imine having Structure CI5, the amide havingStructure AD11 can be utilized when preparing an N-substituted α-chloroimine having Structure CI11, the amide having Structure AD13 can beutilized when preparing an N-substituted α-chloro imine having StructureCI13, and the amide having Structure AD15 can be utilized when preparingan N-substituted α-chloro imine having Structure CI15. R¹, R², D¹, D²,L¹, L², L³, Q¹, q, and r within N-substituted α-chloro imine StructuresCI1-CI5, CI11, CI13, and CI15 are independently described as features ofthe N²-phosphinyl amidine compound Structures NP1-NP10, NP11, NP13,NP15, NP16, NP18, and/or NP20. Since N-substituted α-chloro imineStructures CI1-CI5 can be utilized to prepare embodiments ofN²-phosphinyl amidine compounds having Structures NP1—NP10, NP11, NP13,NP15, NP16, NP18, and/or NP20, the R¹, R², D¹, D², L¹, L², L³, Q¹, q,and r descriptions for the N²-phosphinyl amidine compounds can beutilized without limitation to further describe the N-substitutedα-chloro imine Structures CI1-CI5, CI11, CI13, and CI15.

Generally, phosphorus pentachloride and the amide can be contacted in aphosphorus pentachloride to amide group molar ratio of at least 1:1. Inan embodiment, phosphorus pentachloride and the amide can be contactedin a phosphorus pentachloride to amide group molar ratio of at least1.025:1; alternatively, of at least 1.05:1; or alternatively, of atleast 1.075:1. In some embodiments, phosphorus pentachloride and theamide can be contacted in a phosphorus pentachloride to amide groupmolar ratio ranging from 1:1 to 1.5:1; alternatively, ranging from1.025:1 to 1.30:1; alternatively, ranging from 1.05:1 to 1.25:1; oralternatively, ranging from 1.075:1 to 1.20:1.

In an embodiment, the conditions capable of forming the N-substitutedα-chloro imine can include a temperature of at least 0° C.;alternatively, of at least 5° C.; alternatively, of at least 10° C.; oralternatively, of at least 15° C. In some embodiments, the reactionconditions capable of forming the N-substituted α-chloro imine caninclude a temperature ranging from 0° C. to 160° C.; alternatively,ranging from 5° C. to 150° C.; alternatively, ranging from 10° C. to140° C.; or alternatively, ranging from 15° C. to 130° C.

In some embodiments, the conditions capable of forming the N-substitutedα-chloro imine can include an initial phosphorus and amide contacttemperature and a second temperature to form the N-substituted α-chloroimine. It should be noted the when the conditions capable of forming theN-substituted α-chloro imine is described as occurring at twotemperatures (one for the contact of the initial phosphorus and amideand one for the formation of the amide) that this description does notexclude the prospect that the N-substituted α-chloro imine may be formedat the contact temperature. The description just relates that, in someembodiments, the N-substituted α-chloro imine formation may proceedbetter when the initial contact between the initial phosphorus and amideis performed at one temperature and the formation of the N-substitutedα-chloro imine is completed at a second different temperature.

In an embodiment, the first amine and acid halide can be contacted at atemperature ranging from 0° C. to 60° C.; alternatively, ranging from 5°C. to 50° C.; alternatively, ranging from 10° C. to 45° C.; oralternatively, ranging from 15° C. to 40° C. In an embodiment, the amidecan be formed at a temperature ranging from 20° C. to 160° C.;alternatively, ranging from 30° C. to 150° C.; alternatively, rangingfrom 35° C. to 140° C.; or alternatively, ranging from 40° C. to 130° C.In an embodiment, the conditions capable of forming the amide caninclude a reaction time of at 5 minutes; alternatively, of at least 10minutes; alternatively, of at least 15 minutes; or alternatively, of atleast 20 minutes. In some embodiments, the conditions capable of formingthe N-substituted α-chloro imine can include a reaction time rangingfrom 5 minutes to 6 hours; alternatively, ranging from 10 minutes to 5hours; alternatively, ranging from 15 minutes to 4.5 hours; oralternatively, ranging from 20 minutes to 4 hours.

In an embodiment, the phosphorus pentachloride and the amide can becontacted in an aprotic solvent. In some embodiments, the phosphoruspentachloride and the amide can be contacted in a polar aprotic solvent.Aprotic solvents which can be utilized include hydrocarbon solvents,halogenated hydrocarbon solvents, ether solvents, and any combinationthereof; alternatively, hydrocarbon solvents; alternatively, halogenatedhydrocarbon solvents; or alternatively, ether solvents. Solvents aregenerally disclosed herein and any general or specific aprotic solventand/or polar aprotic solvent described herein can be utilized to furtherdescribe the method of preparing an N-substituted α-chloro imine.

In an embodiment, the N-substituted α-chloro imine can be utilizedwithout further isolation or purification. In some embodiments, theamide can be isolated; alternatively, purified; or alternatively,isolated and purified. In an embodiment, the method can include a stepof isolating the N-substituted α-chloro imine by evaporating the solventin which the N-substituted α-chloro imine is formed. In someembodiments, the method can include a step of isolating theN-substituted α-chloro imine by filtering the solution to removeparticulate materials and/or byproducts of the reaction and evaporatingthe solvent. In some embodiments, the method can include a purificationstep wherein the N-substituted α-chloro imine is purified by dissolvingthe N-substituted α-chloro imine in a solvent and filtering the solutionto remove particulate materials and/or byproducts of the reaction. Thesolvent utilized to purify the N-substituted α-chloro imine can be thesame as the solvent utilized to form the N-substituted α-chloro imine orit can be different than the solvent utilized to form amide. In someembodiments, the method can include a step of purifying theN-substituted α-chloro imine by washing the N-substituted α-chloro iminewith a solvent. In some embodiments, the method can include a step ofpurifying the N-substituted α-chloro imine by distillation. In otherembodiments, the method can include a step of purifying theN-substituted α-chloro imine by recrystallization.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g. at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure. Generally, thedistillation of the N-substituted α-chloro imine can be performed usingany suitable method. In some embodiments, the N-substituted α-chloroimine can be distilled at ambient pressure. In other embodiments, theN-substituted α-chloro imine can be distilled under reduced pressure.

The N-substituted α-chloro imine then can be contacted with a secondamine. In an embodiment, the second amine can have the Structure A5. R³within amine

R³—NH₂  Structure A5

Structure A5 is independently described as a feature of theN²-phosphinyl amidine compounds Structures NP1—NP10, NP11, NP13, NP15,NP16, NP18, and/or NP20. Since amine Structure A5 is utilized to prepareembodiments of N²-phosphinyl amidine compounds having StructuresNP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20 the R³ descriptionfor the N²-phosphinyl amidine compounds can be utilized withoutlimitation to further describe the amine Structure A5. In an embodiment,the second amine can be the same as the first amine. In anotherembodiment, the second amine is different from the first amine Amineshaving Structure A5 are described herein and can be utilized withoutlimitation to further describe the method of preparing the amidinecompound having only one N² hydrogen atom.

Generally, the second amine and N-substituted α-chloro imine can becontacted in a second amine to N-substituted α-chloro imine equivalentratio of at least 0.9:1. In some embodiments, the second amine andN-substituted α-chloro imine can be contacted in a second amine toN-substituted α-chloro imine equivalent ratio of at least 0.95:1;alternatively, of at least 0.975:1; or alternatively, of at least0.99:1. In some embodiments, the second amine and N-substituted α-chloroimine can be contacted in a second amine to N-substituted α-chloro imineequivalent ratio ranging from 0.9:1 to 1.25:1; alternatively, rangingfrom 0.95:1 to 1.20:1; alternatively, ranging from 0.975:1 to 1.15:1; oralternatively, ranging from 0.99:1 to 1.10:1. In other embodiments, thesecond amine and N-substituted α-chloro imine can be contacted in asecond amine to N-substituted α-chloro imine equivalent ratio of about1:1.

In an embodiment, the conditions capable of forming the amidine compoundhaving only one N² hydrogen atom can include a temperature of at least0° C.; alternatively, of at least 5° C.; alternatively, of at least 10°C.; or alternatively, of at least 15° C. In some embodiments, thereaction conditions capable of forming the amidine compound having onlyone N² hydrogen atom includes a temperature ranging from 0° C. to 160°C.; alternatively, ranging from 5° C. to 150° C.; alternatively, rangingfrom 10° C. to 140° C.; or alternatively, ranging from 15° C. to 130° C.

In some embodiments, the conditions capable of forming the amidinecompound having only one N² hydrogen atom can include a second amine andN-substituted α-chloro imine contact temperature and a secondtemperature to form the amidine compound having only one N² hydrogenatom. It should be noted the when the conditions capable of forming theamidine compound having only one N² hydrogen atom is described asoccurring at two temperatures (one for the contact of the second amineand N-substituted α-chloro imine and one for the formation of theamidine compound having only one N² hydrogen atom) that this descriptiondoes not exclude the prospect that the amidine compound having only oneN² hydrogen atom may be formed at the contact temperature. Thedescription just relates that, in some embodiments, the amidine compoundhaving only one N² hydrogen atom formation may precede better when theinitial contact between the second amine and N-substituted α-chloroimine is performed at one temperature and the formation of the amidinecompound having only one N² hydrogen atom is completed at a seconddifferent temperature.

In an embodiment, the second amine and N-substituted α-chloro imine canbe contacted at a temperature ranging from 0° C. to 60° C.;alternatively, ranging from 5° C. to 50° C.; alternatively, ranging from10° C. to 45° C.; or alternatively, ranging from 15° C. to 40° C. In anembodiment, amidine compound having only one N² hydrogen atom can beformed at a temperature ranging from 40° C. to 160° C.; alternatively,ranging from 50° C. to 150° C.; alternatively, ranging from 55° C. to140° C.; or alternatively, ranging from 60° C. to 130° C. In anembodiment, the conditions capable of forming the amidine compoundhaving only one N² hydrogen atom can include a reaction time of at 15minutes; alternatively, of at least 30 minutes; alternatively, of atleast 45 minutes; or alternatively, of at least 1 hour. In someembodiments, the conditions capable of forming the amidine compoundhaving only one N² hydrogen atom can include a reaction time rangingfrom 15 minutes to 36 hours; alternatively, ranging from 30 minutes to30 hours; alternatively, ranging from 45 minutes to 24 hours; oralternatively, ranging from 1 hour to 18 hours.

In an embodiment, the second amine and N-substituted α-chloro imine canbe contacted in an aprotic solvent. In some embodiments, the secondamine and N-substituted α-chloro imine can be contacted in a polaraprotic solvent. Aprotic solvents which can be utilized includehydrocarbon, halogenated hydrocarbon, ethers, and any combinationthereof; alternatively, hydrocarbons, halogenated hydrocarbons, and anycombination thereof; alternatively, hydrocarbons; alternatively,halogenated hydrocarbons; or alternatively, ethers. Solvents aregenerally disclosed herein and any general or specific aprotic solventand/or polar aprotic solvent described herein can be utilized to furtherdescribe the method of preparing the amidine compound having only one N²hydrogen atom.

In an embodiment, the formed amidine compound having only one N²hydrogen atom can be a hydrogen chloride salt of the amidine compoundhaving only one N² hydrogen atom. When the formed amidine compoundhaving only one N² hydrogen atom is a hydrogen chloride salt of theamidine compound having only one N² hydrogen atom, the method ofpreparing the amidine compound having only one N² hydrogen atom furthercomprises a step of neutralizing the hydrogen chloride salt to release anon-ionic amidine compound having only one N² hydrogen atom (e.g. anamidine compound having Structures AM1-AM5, AM11, AM13, and/or AM 15wherein R³ is a non-hydrogen group). In an embodiment, the hydrogenchloride salt of the amidine compound having only one N² hydrogen atomis neutralized by contacting the hydrogen chloride salt of the amidinecompound having only one N² hydrogen atom with an aqueous solution of aGroup 1 or Group 2 metal hydroxide: alternatively, a Group 1 metalhydroxide; alternatively, a group 2 metal hydroxide. In an embodiment,the Group 1 metal hydroxide of the aqueous solution of a Group 1 metalhydroxide can be lithium hydroxide, sodium hydroxide, potassiumhydroxide, rubidium hydroxide, or any combination thereof;alternatively, sodium hydroxide, potassium hydroxide, or any combinationthereof; alternatively, lithium hydroxide; alternatively, sodiumhydroxide; or alternatively, potassium hydroxide.

In an embodiment, the Group 1 or Group 2 metal hydroxide can be addedbefore the hydrogen chloride salt of the amidine compound having onlyone N² hydrogen atom is separated from the solvent utilized to producethe hydrogen chloride salt of the amidine compound having only one N²hydrogen atom. In this scenario, the aqueous Group 1 or Group 2 metalhydroxide can be mixed with the solution comprising the hydrogenchloride salt of the amidine compound having only one N² hydrogen atomand solvent. The aqueous layer and organic layer (comprising thenon-ionic amidine compound having only one N² hydrogen atom and solvent)can then be separated. In some embodiments, an additional solvent iscontacted with the mixture to facilitate the separation of the non-ionicamidine compound having only one N² hydrogen atom from the aqueouslayer. Solvents are generally disclosed herein and any general orspecific aprotic solvent and/or polar aprotic solvent described hereincan be utilized to further describe neutralizing the hydrogen chloridesalt of the amidine compound having only one N² hydrogen atom.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g. at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

In an embodiment, the non-ionic amidine compound having only one N²hydrogen atom can be utilized without further purification. In someembodiments, the non-ionic amidine compound having only one N² hydrogenatom can be purified. In an embodiment, the method can include apurification step of dissolving the non-ionic amidine compound havingonly one N² hydrogen atom in a solvent and filtering the solution toremove particulate materials and/or byproducts of the reaction. Solventsare generally disclosed herein and can be utilized without limitation asthe solvent for washing the non-ionic amidine compound having only oneN² hydrogen atom. In some embodiments, the method can include a step ofpurifying the non-ionic amidine compound having only one N² hydrogenatom by washing non-ionic amidine compound having only one N² hydrogenatom with a solvent. In other embodiments, the method can include a stepof purifying the non-ionic amidine compound having only one N² hydrogenatom by recrystallization.

In an aspect, the steps for preparing the intermediate compounds in thepreparation of the N²-phosphinyl amidine compound (the steps ofpreparing amidine compounds—e.g. amidine compounds having StructuresAM1-AM11, AM13, AM 15, AM 16, AM18, and AM20—from nitriles, amines,compounds capable of abstracting protons, halogenated compounds, acidchlorides, and/or phosphorus pentachloride) can be included in theprocess for producing the N²-phosphinyl amidine compounds of thisdisclosure. These intermediate steps are disclosed herein and may becombined in an appropriate fashion to describe a method of preparing theN²-phosphinyl amidine compound. When the steps are combined, appropriatestep identifiers (e.g. 1), 2), etc. . . . , a), b), etc. . . . , or i),ii), etc. . . . ) and compound/solvent identifiers (e.g. first, second,etc. . . . ) can be added to indicate individual and/or differentsteps/compounds/solvents utilized within the preparation of the amidinecompound without detracting from the general disclosure.

Generally, the methods for forming the amide, the N-substituted α-chloroimine, the amidine compound, the metal amidinate, and the N²-phosphinylamidine compound can combined in various embodiments to provide a methodto form an N²-phosphinyl amidine compound having only one N² hydrogenatom utilizing amines, acid halides, compounds capable of abstracting aproton from the —NH₂ group, and phosphine halides. In a non-limitingembodiment, a method of preparing an N²-phosphinyl amidine compound cancomprise: a) contacting a first amine and an acid halide; b) forming anamide c) contacting the amide with phosphorus pentachloride; d) formingan N-substituted α-chloro imine; e) contacting the N-substitutedα-chloro imine with a second amine; f) forming an amidine compoundhaving only one N² hydrogen atom; g) isolating the amidine compoundhaving only one N² hydrogen atom; h) contacting the amidine compoundhaving only one N² hydrogen atom with a compound capable of abstractinga proton from the amidine compound having only one N² hydrogen atom; i)forming a metal amidinate; j) contacting the metal amidinate and aphosphine halide; and k) forming the N²-phosphinyl amidine compound.These methods can contain steps other than those recited in the methodsof preparing the amide described herein, methods of preparing theN-substituted α-chloro imine described herein, methods of preparingamidine compounds described herein, methods of preparing the metalamidinate described herein, and methods of preparing N²-phosphinylamidine compounds described herein which can be utilized to furtherdescribe these methods. Additional features of each of these steps (e.g.reagent ratios, formation conditions, among other considerations) aredescribed herein and may be utilized to further describe the methods.

In an aspect, this disclosure relates to a method of preparing anN²-phosphinyl amidine metal salt complex. Generally, the method ofpreparing the N²-phosphinyl amidine metal salt complex can comprise: a)contacting a metal salt with an N²-phosphinyl amidine compound; and b)forming the N²-phosphinyl amidine metal salt complex. Generally, theN²-phosphinyl amidine metal salt complex can be formed under conditionscapable of forming an N²-phosphinyl amidine metal salt complex. In someembodiments, the N²-phosphinyl amidine metal salt complex can beisolated; alternatively, purified; or alternatively, isolated andpurified.

N²-phosphinyl amidine compounds are disclosed herein and can be utilizedwithout limitation to further describe the method of preparing anN²-phosphinyl amidine metal salt complex. Metal salts are disclosedherein and can be utilized without limitation to further describe themethod of preparing an N²-phosphinyl amidine metal salt complex.

Generally, the metal salt and the N²-phosphinyl amidine compound can becontacted at a metal salt to N²-phosphinyl amidine compound equivalentratio of at least 0.9:1. In some embodiments, the metal salt and theN²-phosphinyl amidine compound can be contacted at a metal salt toN²-phosphinyl amidine compound equivalent ratio of at least 0.95:1;alternatively, of at least 0.975:1; or alternatively, of at least0.99:1. In some embodiments, the metal salt and the N²-phosphinylamidine compound can be contacted at a metal salt to N²-phosphinylamidine compound equivalent ratio ranging from 0.9:1 to 1.25:1;alternatively, ranging from 0.95:1 to 1.20:1; alternatively, rangingfrom 0.975:1 to 1.15:1; or alternatively, ranging from 0.99:1 to 1.10:1.In other embodiments, the metal salt and the N²-phosphinyl amidinecompound can be contacted at a metal salt to N²-phosphinyl amidinecompound equivalent ratio of about 1:1.

In an embodiment, the conditions capable of forming an N²-phosphinylamidine metal salt complex can include a contact temperature of at least0° C.; alternatively, of at least 5° C.; alternatively, of at least 10°C.; or alternatively, of at least 15° C. In some embodiments, theconditions capable of forming the N²-phosphinyl amidine metal saltcomplex can include a contact temperature ranging from 0° C. to 60° C.;alternatively, ranging from 5° C. to 50° C.; alternatively, ranging from10° C. to 45° C.; or alternatively, ranging from 15° C. to 40° C. In anembodiment, the conditions capable of forming the N²-phosphinyl amidinemetal salt complex can include a contact time of at least 15 minutes;alternatively, of at least 30 minutes; alternatively, of at least 45minutes; or alternatively, of at least 1 hour. In some embodiments, theconditions capable of forming the N²-phosphinyl amidine metal saltcomplex can include a contact time ranging from 15 minutes to 36 hours;alternatively, ranging from 30 minutes to 30 hours; alternatively,ranging from 45 minutes to 24 hours; or alternatively, ranging from 1hour to 18 hours.

In an embodiment, the metal salt and the N²-phosphinyl amidine compoundcan be contacted in a solvent. In some embodiments, the metal salt andthe N²-phosphinyl amidine compound can be contacted in a polar solvent.In some embodiments, the solvent is the same as the neutral ligand, Q,within some embodiments of the N²-phosphinyl amidine metal salt complex.Solvents (general and specific) are generally disclosed herein and canbe utilized, without limitation, to further describe the method ofpreparing the N²-phosphinyl amidine metal salt complex.

In an embodiment, the N²-phosphinyl amidine metal salt complex can beutilized without further isolation or purification. In some embodiments,the N²-phosphinyl amidine metal salt complex can be isolated;alternatively, purified; or alternatively, isolated and purified. In anembodiment, wherein the N²-phosphinyl amidine metal salt complex isprepared in a solvent, the method to prepare the N²-phosphinyl amidinemetal salt complex can include a step of isolating the N²-phosphinylamidine metal salt complex by evaporating the solvent. In an embodimentwherein the N²-phosphinyl amidine metal salt complex is prepared in asolvent, the method to prepare the N²-phosphinyl amidine metal saltcomplex can include the step of isolating the N²-phosphinyl amidinemetal salt complex by filtering the solution to remove particulatematerials and/or byproducts of the reaction and evaporating the solvent.In embodiments, the method to prepare the N²-phosphinyl amidine metalsalt complex can include a purification step wherein the N²-phosphinylamidine compound is purified by dissolving the N²-phosphinyl amidinemetal salt complex in a solvent and filtering the solution to removeparticulate materials and/or byproducts of the reaction. The solventutilized to purify the N²-phosphinyl amidine metal salt complex can bethe same a solvent utilized to form the N²-phosphinyl amidine metal saltcomplex or it can be different than the solvent utilized to form theN²-phosphinyl amidine metal salt complex. In some embodiments, themethod of preparing the N²-phosphinyl amidine metal salt complex caninclude a purification step of isolating the N²-phosphinyl amidine metalsalt complex by washing the N²-phosphinyl amidine metal salt complexwith a solvent. In other embodiments, the method of preparing theN²-phosphinyl amidine metal salt complex can include a purification stepof recrystallizing the N²-phosphinyl amidine metal salt complex.

Generally, the evaporation of the solvent can be performed using anysuitable method. In some embodiments, the solvent can be evaporated atambient temperature (15-35° C.—no applied external heat source). Inother embodiments, the solvent can be evaporated with gentle heating(e.g. at a temperature ranging from 25° C. to 50° C.). In furtherembodiments, the solvent can be evaporated at ambient temperature underreduced pressure. In yet other embodiments, the solvent can beevaporated with gentle heating under reduced pressure.

It has been unexpectedly discovered that the time between the isolationand/or purification of the N²-phosphinyl amidine metal salt complex andthe formation of the oligomerization catalyst system can have an impacton aspects of the oligomerization. Firstly, it has been observed thatincreasing the time between the isolation and/or purification of theN²-phosphinyl amidine metal salt complex and the formation of theoligomerization catalyst system can increase the catalytic activityand/or increase the productivity of the catalyst system. Secondly, ithas been observed that increasing the time between the isolation and/orpurification of the N²-phosphinyl amidine metal salt complex and theformation of the oligomerization catalyst system can increase thepercentage of polymer produced by the oligomerization catalyst system.Without being limited by theory, it is believed that these effectsresult from the disassociation of (or alternatively, evaporation of)neutral ligand, Q, from the N²-phosphinyl amidine metal salt complexand/or from the crystal lattice of the N²-phosphinyl amidine metal saltcomplex.

Controlling the time between the isolation and/or purification of theN²-phosphinyl amidine metal salt complex and the formation of theoligomerization catalyst system can improve the olefin oligomerizationprocess. For instance, one can increase the activity and/or productivityof the catalyst system by increasing the time between the isolationand/or purification of the N²-phosphinyl amidine metal salt complex andformation of the oligomerization catalyst system. Increasing theactivity and/or the productivity of the catalyst system can provideincreased olefin oligomer product per unit of catalyst system.

However, it may not be possible to increase the time between theisolation and/or purification of the N²-phosphinyl amidine metal saltcomplex and formation of the oligomerization catalyst systemindiscriminately. As noted herein, increasing the time between theisolation and/or purification of the N²-phosphinyl amidine metal saltcomplex and the formation of the oligomerization catalyst system canincrease the percentage of polymer produced by the oligomerizationcatalyst system. If the polymer production of the catalyst systemutilizing the N²-phosphinyl amidine metal salt complex increases toomuch, polymer production can adversely impact the oligomerizationprocess. For example, polymer could adhere to the oligomerizationreactor walls or cooling apparatus and cause fouling which cannecessitate a reactor shut down to remove the polymer. Consequently,there can be a need to balance increases in catalyst system activityand/or productivity against increased polymer production.

It has also been discovered that at least some of the effects ofincreasing the time between the isolation and/or purification of theN²-phosphinyl amidine metal salt complex and the formation of theoligomerization catalyst system can be reversed by adding a neutralligand to the N²-phosphinyl amidine metal salt complex. The ability toreverse some of the effects of increasing the time between the isolationand/or purification of the N²-phosphinyl amidine metal salt complex andthe formation of the oligomerization catalyst system can reducepotentially negative effects. Non-limiting examples of negative effectsof increasing the time between the isolation and/or purification of theN²-phosphinyl amidine metal salt complex and the formation of theoligomerization catalyst system can include 1) prohibiting the abilityto use an N²-phosphinyl amidine metal salt complex by increasing thetime between the isolation and/or purification of the N²-phosphinylamidine metal salt complex and the formation of the oligomerizationcatalyst system to a point wherein the formed catalyst system producesan undesirable quantity of polymer and 2) reducing the need to minimizethe time between preparing the N²-phosphinyl amidine metal salt complexand the preparation of the catalyst system utilizing the N²-phosphinylamidine metal salt complex.

However, it has also been discovered that too much neutral ligandassociated with the N²-phosphinyl amidine metal salt complex cansignificantly reduce or eliminate the catalyst system olefin oligomerproductivity. Consequently, it can be necessary to take precautions tocontrol the amount of neutral ligand provided to the N²-phosphinylamidine metal salt complex. Generally, addition of the neutral ligand tothe N²-phosphinyl amidine metal salt complex can be accomplished by anysuitable method. For example, the N²-phosphinyl amidine metal saltcomplex can be recrystallized from a solution containing a neutralligand or the N²-phosphinyl amidine metal salt complex can be placed ina solvent containing a neutral ligand. Excess neutral ligand can beremoved from the N²-phosphinyl amidine metal salt complex by allowingthe solvent to evaporate or by increasing the time between the treatmentof the N²-phosphinyl amidine metal salt complex with the neutral ligandand the formation of the oligomerization catalyst system.

In an embodiment the isolated and/or purified N²-phosphinyl amidinemetal salt complex can be utilized in an olefin oligomerization process.In an embodiment, the olefin oligomerization process can comprise: a)forming a composition comprising an N²-phosphinyl amidine metal saltcomplex; b) forming a mixture comprising an olefin and a metal alkyl; c)contacting the composition of step a) and the mixture of step b); and d)forming an olefin oligomer product. In an embodiment, the olefinoligomerization process can comprise: a) forming a compositioncomprising an N²-phosphinyl amidine metal salt complex; b) forming amixture comprising an olefin, a metal alkyl, and hydrogen; c) contactingthe composition of step a) and the mixture of step b); and d) forming anolefin oligomer product. In some embodiments, the mixture comprising theolefin and the metal alkyl can also comprise hydrogen. In someembodiments the composition comprising the N²-phosphinyl amidine metalsalt complex also can comprise a solvent (e.g., a first solvent). Insome embodiments, the mixture comprising an olefin, a metal alkyl, andoptionally hydrogen, also can comprise a solvent (e.g., a secondsolvent). In an embodiment, the solvents used in the compositioncomprising the N²-phosphinyl amidine metal salt complex and the mixturecomprising the olefin and the metal alkyl (and optionally hydrogen) canbe the same; or can be different. The N²-phosphinyl amidine metal saltcomplex, metal alkyl, olefin, solvents, and features of the olefinoligomer are independently described herein and can be utilized, withoutlimitation to further describe the olefin oligomerization process. Insome embodiments, the metal alkyl can comprise an aluminoxane. Ratiosfor the metal of the N²-phosphinyl amidine metal salt complex to themetal of the metal alkyl are provided herein and can be utilized withoutlimitation to further describe the olefin oligomerization process.

In an aspect, any method of producing a catalyst system disclosed hereinor any method of oligomerizing or polymerizing an olefin can furthercomprise a step of aging the N²-phosphinyl amidine metal salt complex.In another aspect, any method of producing a catalyst system disclosedherein or any method of oligomerizing or polymerizing an olefin canfurther comprise a step of treating the N²-phosphinyl amidine metal saltcomplex with a neutral ligand; or alternatively, 1) treating theN²-phosphinyl amidine metal salt complex with a neutral ligand and 2)allowing the treated N²-phosphinyl amidine metal salt complex to age. Inanother aspect, any method of producing a catalyst system disclosedherein or any method of oligomerizing or polymerizing an olefin canfurther comprise a step of treating an aged N²-phosphinyl amidine metalsalt complex with a neutral ligand; or alternatively, 1) treating theN²-phosphinyl amidine metal salt complex with a neutral ligand and 2)allowing the treated N²-phosphinyl amidine metal salt complex to age.

In an aspect, the activity of any olefin oligomerization methoddescribed herein (using any catalyst system described herein comprisingany N²-phosphinyl amidine metal salt complex described herein) can becontrolled by aging the N²-phosphinyl amidine metal salt complex. In anaspect, the activity of any olefin oligomerization method describedherein (using any catalyst system as described herein comprising anyN²-phosphinyl amidine metal salt complex described herein) can becontrolled by treating the N²-phosphinyl amidine metal salt complex witha neutral ligand; or alternatively, 1) treating the N²-phosphinylamidine metal salt complex with a neutral ligand and 2) allowing thetreated N²-phosphinyl amidine metal salt complex to age. In an aspect,the activity of any olefin oligomerization method described herein(using any catalyst system described herein comprising any N²-phosphinylamidine metal salt complex described herein) can be controlled bytreating an aged N2-phosphinyl amidine metal salt complex with a neutralligand; or alternatively, 1) treating the N²-phosphinyl amidine metalsalt complex with a neutral ligand and 2) allowing the treatedN²-phosphinyl amidine metal salt complex to age.

The catalytic activity of any catalyst system described hereincomprising any N²-phosphinyl amidine metal salt complex described hereinin an olefin oligomerization process can be defined as the grams ofolefin oligomer product (or liquid olefin oligomer product, or any otherdefined portion of the olefin oligomerization product) produced per gramof metal of the metal salt in the N²-phosphinyl amidine metal saltcomplex utilized. In an embodiment, the catalyst system activity of anycatalyst system described herein comprising any N²-phosphinyl amidinemetal salt complex described herein can be increased by utilizing anaged N²-phosphinyl amidine metal salt complex. This activity increasecan be described as a percentage increase in the catalyst systemactivity and can be related to the activity of the catalyst systemprepared using a fresh N²-phosphinyl amidine metal salt complex, a₀.Generally, a fresh N²-phosphinyl amidine metal salt complex is one whichhas been utilized to prepare an oligomerization catalyst system within14 days of its isolation and/or purification. It should be noted, afresh N²-phosphinyl amidine metal salt complex does not contain excessneutral ligand which can give an inactive olefin oligomerizationcatalyst system (i.e. a catalyst system that produces less than 550grams oligomer per gram metal of metal salt in the N²-phosphinyl amidinemetal salt complex). The activity of the catalyst system based upon anaged N²-phosphinyl amidine metal salt complex can be denoted a_(x).

In an embodiment, the N²-phosphinyl amidine metal salt complex can beaged for up to 24 months; alternatively, up to 18 months; alternatively,up to 15 months; alternatively, up to 12 months; alternatively, up to 11months; alternatively, up to 10 months; alternatively, up to 9 months;alternatively, up to 8 months; alternatively, up to 7 months; oralternatively, up to 6 months. In an embodiment, aging the N²-phosphinylamidine metal salt complex (for any time period described herein) canincrease the activity of any catalyst system described herein utilizingany N²-phosphinyl amidine metal salt complex described herein at least10%; alternatively, by at least 20%; alternatively, by at least 30%;alternatively, by at least 40%; or alternatively, at least 50%. In someembodiments, aging the N²-phosphinyl amidine metal salt complex (for anytime period described herein) can increase the activity of any catalystsystem described herein utilizing any N²-phosphinyl amidine metal saltcomplex described herein from 10 to 1500%; alternatively, from 20% to1000%; alternatively, from 30 to 750%; alternatively, from 40 to 600%;or alternatively, from 50 to 500%.

In an embodiment, aging the N²-phosphinyl amidine metal salt complex(for any time period described herein) for any catalyst system describedherein utilizing any N²-phosphinyl amidine metal salt complex describedherein can provide a catalyst system which can produce any definedpercentage of polymer described herein. In an embodiment, aging theN²-phosphinyl amidine metal salt complex (for any time period describedherein) for any catalyst system described herein utilizing anyN²-phosphinyl amidine metal salt complex described herein can provide acatalyst system can provide a catalyst system which can produce lessthan 5 weight percent polymer; alternatively, equal to or less than 2weight % polymer; alternatively, equal to or less than 1.5alternatively, equal to or less than 1 weight % polymer; alternatively,equal to or less than 0.75 alternatively, equal to or less than 2 weight% polymer; alternatively, equal to or less than 0.5 weight % polymer;alternatively, equal to or less than 0.4 weight % polymer;alternatively, equal to or less than 0.3 weight % polymer;alternatively, equal to or less than 0.2 weight % polymer; or,alternatively, equal to or less than 0.1 weight % polymer. Generally,the basis for weight percent polymer is based upon all products of theolefin oligomerization (excluding unreacted monomer, catalyst systemcomponents, solvent, and other non-olefin oligomerization products).

In some embodiments, any catalyst system described herein utilizing anaged N²-phosphinyl amidine metal salt complex can have a combination ofany increased activity described herein and any amount of polymerdescribed herein. The catalyst system described herein utilizing an agedN²-phosphinyl amidine metal salt complex can further be describedutilizing, individually or in any combination, any other catalyst systemfeature or olefin oligomerization product feature described herein.

In an embodiment, a calibration curve can be produced depictingcatalytic activity and or polymer product of any catalyst systemdescribed herein comprising any N²-phosphinyl amidine metal salt complexdescribed herein in response to aging the phosphinyl amidine metal saltcomplex. In some embodiments, a calibration curve (for catalyst activityand/or polymer production) can be depicted as a function of the periodof N²-phosphinyl amidine metal salt complex age in order to derive apredictive equation. The calibration curve or predictive equationrelating catalyst system activity and/or polymer production in responseto N²-phosphinyl amidine metal salt complex age can be utilized toadjust one or more user and/or process parameters based upon theinterpolation or extrapolation the calibration curve and/or thepredictive equation. It is contemplated that in some aspects, the extentto which a_(x) increases with respect to a₀ can fall outside theinstantly disclosed ranges and can be larger than would be expectedbased on the presently disclosed values depending on the conditionsunder which the N²-phosphinyl amidine metal salt complex is aged. Forexample, the N²-phosphinyl amidine metal salt complex can be subjectedto aging for time periods that are 5 to 10 times longer than thosepresently recited or under conditions of elevated temperature and/orreduced pressure. The effects of aging the N²-phosphinyl amidine metalsalt complex under such conditions can be subject to the hereinmentioned analysis to provide predictive information that can lead oneto conditions under which aging the N²-phosphinyl amidine metal saltcomplex can increase catalyst system activity using an agedN²-phosphinyl amidine metal salt complexes outside of the recitednumerical ranges. It is contemplated that given the benefits of thisdisclosure and using routine experimentation one having ordinary skillin the art can modify the methodologies disclosed herein to alter thecatalytic system activity using an aged N²-phosphinyl amidine metal saltcomplexes to a desired value or range. Such modifications fall withinthe scope of this disclosure.

In an embodiment, contacting of the N²-phosphinyl amidine metal saltcomplex (aged or otherwise) with a neutral ligand can be carried outusing any suitable molar ratio of neutral ligand to N²-phosphinylamidine metal salt. In an embodiment, the molar ratio neutral ligand toN²-phosphinyl amidine metal salt complex can be at least 0.2:1;alternatively, at least 0.3:1; alternatively, at least 0.4:1; oralternatively, at least 0.5:1. In an embodiment, the molar ratio neutralligand to N²-phosphinyl amidine metal salt complex can be from 0.2:1 to10,000:1; alternatively, 0.3:1 to 8,000:1; alternatively, from 0.4:1 to6,000:1; or alternatively, from 0.5:1 to 5,000:1. In an embodiment, thecontact of the N²-phosphinyl amidine metal salt complex can occur in asolvent consisting essentially of the neutral ligand; or alternatively,in a solvent comprising, or consisting essentially of, the neutralligand and a non-complexing solvent.

When the N²-phosphinyl amidine metal salt complex is contacted with asolvent consisting essentially of the neutral ligand, the molar ratio ofneutral ligand to N²-phosphinyl amidine metal salt can be any molarratio of neutral ligand to N²-phosphinyl amidine metal salt disclosedherein. In other embodiments wherein the N²-phosphinyl amidine metalsalt complex is contacted with a solvent consisting essentially of theneutral ligand, the molar ratio of neutral ligand to N²-phosphinylamidine metal salt can be any molar ratio of neutral ligand toN²-phosphinyl amidine metal salt can be at least 5:1; alternatively, atleast 7.5:1; alternatively, at least 10:1; alternatively, at least 10:1;alternatively, at least 15:1; alternatively, 5:1; alternatively, rangefrom 7.5:1 to 10,000:1; alternatively, range from 10:1 to 8,000:1;alternatively, range from 10:1 to 6,000:1; or alternatively, range from15:1 to 5,000:1.

When the N²-phosphinyl amidine metal salt complex is contacted with asolvent comprising, or consisting essentially of, the neutral ligand anda non-complexing solvent, the molar ratio of neutral ligand toN²-phosphinyl amidine metal salt can be any molar ratio of neutralligand to N²-phosphinyl amidine metal salt disclosed herein. In otherembodiments wherein the N²-phosphinyl amidine metal salt complex iscontacted with a solvent comprising, or consisting essentially of, theneutral ligand and a non-complexing solvent, the molar ratio of neutralligand to N²-phosphinyl amidine metal salt can be less than or equal to500:1; less than or equal to 300:1; less than or equal to 200:1;alternatively, less than or equal to 100:1; alternatively, range from0.2:1 to 500:1; alternatively, range from 0.3:1 to 300:1; alternatively,range from 0.4:1 to 200:1; or alternatively, from 0.5:1 to 100:1. Insome embodiments, wherein the N²-phosphinyl amidine metal salt complexis contacted with a solvent comprising, or consisting essentially of,the neutral ligand and a non-complexing solvent, the volumetric ratio ofneutral ligand to non-complexing solvent can range from 1:1 to 10,000:1;alternatively, range from 5:1 to 8,000:1; alternatively, range from7.5:1 to 6,000:1; or alternatively, range from 10:1 to 5,000:1.

In an embodiment, the neutral ligand can be any neutral ligand disclosedherein. In some embodiments, the neutral ligand utilized to treat theN²-phosphinyl amidine metal salt complex can be the same as the neutralligand of the N²-phosphinyl amidine metal salt complex; oralternatively, the neutral ligand utilized to treat the N²-phosphinylamidine metal salt complex can be different from the neutral ligand ofthe N²-phosphinyl amidine metal salt complex. In an embodiment, thenon-complexing solvent utilized in an embodiment comprising, orconsisting essentially of, a neutral ligand and a non-complexing solventcan be a hydrocarbon or a halogenated hydrocarbon; alternatively, ahydrocarbon or a halogenated hydrocarbon. Hydrocarbon and halogenatedhydrocarbon solvents (general and specific) are disclosed herein and canbe utilized, without limitation, to further describe any aspect and/orembodiment utilizing a solvent comprising, or consisting essentially of,a neutral ligand and a non-complexing solvent.

In an embodiment, the N²-phosphinyl amidine metal salt complex can beaged (whether or not it has been treated with a neutral ligand)utilizing any suitable methodology. In some embodiments, theN²-phosphinyl amidine metal salt complex can be aged (whether or not ithas been treated with a neutral ligand) at ambient temperature (15-35°C.—no applied external heat source); or alternatively, at ambienttemperature under an inert atmosphere. In other embodiments, theN²-phosphinyl amidine metal salt complex can be aged (whether or not ithas been treated with a neutral ligand) with gentle heating (e.g., at atemperature ranging from 25° C. to 50° C.); alternatively, under reducedpressure; alternatively, ambient temperature under reduced pressure; oralternatively, with gentle heating under reduced pressure.

In an embodiment, the aged N²-phosphinyl amidine metal salt complex, theneutral ligand treated N²-phosphinyl amidine metal salt complex, or theneutral ligand treated and aged N²-phosphinyl amidine metal salt complexcan be utilized in a catalyst system, utilized in a process to prepare acatalyst, and/or a method to oligomerize (or polymerize) an olefin.Generally, the steps of aging the N²-phosphinyl amidine metal saltcomplex, the steps of treating the N²-phosphinyl amidine metal saltcomplex with a neutral ligand, and/or treating the N²-phosphinyl amidinemetal salt complex with a neutral ligand and aging the neutral ligandtreated the N²-phosphinyl amidine metal salt complex can be utilized,without limitation, to further describe the catalyst system, the methodof preparing the catalyst system, and/or the method to oligomerize (orpolymerize) an olefin.

In an aspect, the step(s) for preparing the N²-phosphinyl amidinecompound can be incorporated into the preparation of the N²-phosphinylamidine metal salt complex. When the steps are combined, appropriatestep identifiers (e.g. 1), 2), etc. . . . , a), b), etc. . . . , or i),ii), etc. . . . ) and compound/solvent identifiers (e.g. first, second,etc. . . . ) can be added to indicate individual and/or differentsteps/compounds/solvents utilized within the preparation of the amidinecompound without detracting from the general disclosure.

In an aspect, the present disclosure relates to an olefinoligomerization process; or alternatively, an olefin polymerizationprocess. Within this disclosure, olefin oligomerization relates toprocesses which produce products of which at least 80 weight percentcontain from 1 to 20 monomer units. Within this disclosure, olefinpolymerization relates to process(es) which produces products of whichat least 80 weight percent contain greater than 20 monomer units.

In an embodiment, the olefin oligomerization process can comprise: a)contacting an olefin and a catalyst system; and b) forming an olefinoligomer product. In some embodiments, the olefin oligomerizationprocess can comprise, a) contacting an olefin, hydrogen, and a catalystsystem; and b) forming an olefin oligomer product. In an embodiment, theolefin polymerization process can comprise: a) contacting an olefin anda catalyst system; and b) forming an olefin polymer product. In someembodiments, the olefin polymerization process can comprise a)contacting an olefin, hydrogen, and a catalyst system and b) forming anolefin polymer product. The catalyst system, olefin, and features of theolefin oligomer or olefin polymer product are independently describedherein and can be utilized, without limitation to further describe theolefin oligomerization or olefin polymerization process. In anembodiment, the catalyst system can be prepared in a first solvent. Inan embodiment, the olefin, catalyst system, and optionally hydrogen, canbe contacted in a second solvent. Generally, a solvent in which thecatalyst system can be prepared and the solvent in which the olefin andcatalyst system can be contacted can be the same; or alternatively, canbe different.

In an embodiment, the olefin oligomerization process can comprise: a)forming a catalyst system mixture comprising an N²-phosphinyl amidinemetal salt complex and a metal alkyl; b) contacting the catalyst systemmixture with an olefin; and c) forming an olefin oligomer product. In anembodiment, the olefin polymerization process can comprise: a) forming acatalyst system mixture comprising an N²-phosphinyl amidine metal saltcomplex and a metal alkyl; b) contacting the catalyst system mixturewith an olefin; and c) forming an olefin oligomer product. In someembodiments, the step of contacting the catalyst system mixture with theolefin can be a step of contacting the catalyst system mixture with anolefin and hydrogen. In some embodiments, the catalyst system mixturecan further comprise a solvent (e.g. a first solvent). In someembodiments, the catalyst system mixture and olefin can be contacted ina solvent (e.g. a second solvent when the catalyst system is prepared ina solvent). In an embodiment, the olefin oligomerization process cancomprise: a) forming a catalyst system mixture comprising, or consistingessentially of, an N²-phosphinyl amidine metal salt complex, a metalalkyl, and a first solvent; b) contacting the catalyst system mixturewith an olefin and a second solvent; and c) forming an olefin oligomerproduct. In an embodiment, the olefin polymerization process cancomprise: a) forming a catalyst system mixture comprising, or consistingessentially of, an N²-phosphinyl amidine metal salt complex, a metalalkyl, and a first solvent; b) contacting the catalyst system mixturewith an olefin and a second solvent; and c) forming an olefin oligomerproduct. In some embodiments, the step of contacting the catalyst systemmixture with the olefin and the second solvent can be a step ofcontacting the catalyst system mixture with an olefin, a second solvent,and hydrogen. The N²-phosphinyl amidine metal salt complex, metal alkyl,olefin, solvents, and features of the olefin oligomer or olefin polymerproduct are independently described herein (among other catalyst systemand olefin oligomerization or polymerization features) and can beutilized, without limitation to further describe the olefinoligomerization or olefin polymerization process. In some embodiments,the first and second solvent can be the same; or alternatively, thefirst and second solvent can be different. In some embodiments, themetal alkyl can comprise, or consist essentially of, an aluminoxane.Ratios for the metal of the N²-phosphinyl amidine metal salt complex tothe metal of the metal alkyl are independently provided herein (amongother catalyst system and olefin oligomerization or polymerizationfeatures) and can be utilized without limitation to further describe theolefin oligomerization or olefin polymerization process.

In an embodiment, the olefin oligomerization process can comprise: a)forming a composition comprising an N²-phosphinyl amidine metal saltcomplex; b) forming a mixture comprising an olefin and a metal alkyl; c)contacting the composition of step a) and the mixture of step b); and d)forming an olefin oligomer product. In an embodiment, the olefinpolymerization process can comprise: a) forming a composition comprisinga the N²-phosphinyl amidine metal salt complex; b) forming a mixturecomprising an olefin and a metal alkyl; c) contacting the composition ofstep a) and the mixture of step b); and d) forming an olefin polymerproduct. In some embodiments, the mixture comprising the olefin and themetal alkyl can further comprise hydrogen. In some embodiments thecomposition comprising the N²-phosphinyl amidine metal salt complex canfurther comprise a solvent (e.g. a first solvent). In some embodiments,the mixture comprising an olefin, a metal alkyl, and optionallyhydrogen, can further comprise a solvent (e.g. a second solvent). In anembodiment, the olefin oligomerization process can comprise: a) forminga composition comprising, or consisting essentially of, an N²-phosphinylamidine metal salt complex and a first solvent; b) forming a mixturecomprising an olefin, a metal alkyl, hydrogen, and a second solvent; c)contacting the composition of step a) and the mixture of step b); and d)forming an olefin oligomer product. In an embodiment, the olefinpolymerization process can comprise: a) forming a compositioncomprising, or consisting essentially of, a the N²-phosphinyl amidinemetal salt complex and a first solvent; b) forming a mixture comprisingan olefin, a metal alkyl, hydrogen, and a second solvent; c) contactingthe composition of step a) and the mixture of step b); and d) forming anolefin polymer product. In an embodiment, the solvents used in thecomposition comprising the N²-phosphinyl amidine metal salt complex andthe mixture comprising the olefin and the metal alkyl (and optionallyhydrogen) can be the same; or alternatively, can be different. TheN²-phosphinyl amidine metal salt complex, metal alkyl, olefin, solvents,and features of the olefin oligomer or olefin polymer product (amongother catalyst system and olefin oligomerization or polymerizationfeatures) are independently described herein and can be utilized,without limitation to further describe the olefin oligomerization orolefin polymerization process. In some embodiments, the metal alkyl cancomprise an aluminoxane. Ratios for the metal of the N²-phosphinylamidine metal salt complex to the metal of the metal alkyl areindependently provided herein (among other catalyst system and olefinoligomerization or polymerization features) and can be utilized withoutlimitation to further describe the olefin oligomerization or olefinpolymerization process.

In an embodiment, the olefin oligomerization process can comprise: a)forming a catalyst system mixture comprising an N²-phosphinyl amidinecompound, a metal salt, and a metal alkyl; b) contacting the catalystsystem mixture with an olefin; and c) forming an olefin oligomerproduct. In an embodiment, the olefin polymerization process cancomprise: a) forming a catalyst system mixture comprising anN²-phosphinyl amidine compound, a metal salt, and a metal alkyl; b)contacting the catalyst system mixture with an olefin; and c) forming anolefin oligomer product. In some embodiments, the step of contacting thecatalyst system mixture with the olefin can be a step of contacting thecatalyst system mixture with an olefin and hydrogen. In someembodiments, the catalyst system mixture can further comprise a solvent(e.g. a first solvent). In some embodiments, the catalyst system mixtureand olefin can be contacted in a solvent (e.g. a second solvent when thecatalyst system is prepared in a solvent). In an embodiment, the olefinoligomerization process can comprise: a) forming a catalyst systemmixture comprising, or consisting essentially of, an N²-phosphinylamidine compound, a metal salt, a metal alkyl, and a first solvent; b)contacting the catalyst system mixture with an olefin and a secondsolvent; and c) forming an olefin oligomer product. In an embodiment,the olefin polymerization process can comprise: a) forming a catalystsystem mixture comprising, or consisting essentially of an N²-phosphinylamidine compound, a metal salt, a metal alkyl, and a first solvent; b)contacting the catalyst system mixture with an olefin and a secondsolvent; and c) forming an olefin polymer product. In some embodiments,the step of contacting the catalyst mixture with the olefin and thesecond solvent can be a step of contacting the catalyst system mixturewith an olefin, a second solvent, and hydrogen. In some embodiments, thefirst and second solvent can be the same; or alternatively, the firstand second can be different. The N²-phosphinyl amidine compound, metalsalt, metal alkyl, olefin, solvents, and features of the olefin oligomeror olefin polymer product are independently described herein (amongother catalyst system and olefin oligomerization or polymerizationfeatures) and can be utilized, without limitation to further describethe olefin oligomerization or olefin polymerization process. In someembodiments, the first and second solvent can be the same; oralternatively, the first and second solvent can be different. In someembodiments, the metal alkyl can comprise, or consist essentially of, analuminoxane. The N²-phosphinyl amidine compound, metal salt, metalalkyl, olefin, solvents, and features of the olefin oligomer or olefinpolymer product are independently described herein (among other catalystsystem and olefin oligomerization or polymerization features) and can beutilized, without limitation to further describe the olefinoligomerization or olefin polymerization process. Ratios for theN²-phosphinyl amidine compound to metal salt and ratios for the metal ofthe metal alkyl to metal of the metal salt are independently providedherein (among other catalyst system and olefin oligomerization orpolymerization features) and can be utilized without limitation tofurther describe the olefin oligomerization or olefin polymerizationprocess.

In an embodiment, the olefin oligomerization process can comprise: a)forming a composition comprising an N²-phosphinyl amidine compound and ametal salt; b) forming a mixture comprising an olefin and a metal alkyl;c) contacting the composition formed in step a) and the mixture formedin step b); and d) forming an olefin oligomer product. In an embodiment,the olefin polymerization process can comprise: a) forming a mixturecomprising an N²-phosphinyl amidine compound and a metal salt; b)forming a mixture comprising an olefin and a metal alkyl; c) contactingthe composition formed in step a) and the mixture formed in step b); andd) forming an olefin polymer product. In some embodiments, the mixturecomprising an olefin and a metal alkyl can further comprise hydrogen. Insome embodiments, the composition of step a) can further comprise asolvent (e.g. a first solvent). In some embodiments, the mixture of stepb) can further comprise a solvent (e.g. a second solvent when thecatalyst system is prepared in a solvent). In an embodiment, the olefinoligomerization process can comprise: a) forming a compositioncomprising, or consisting essentially of, an N²-phosphinyl amidinecompound, a metal salt, and a first solvent; b) forming a mixturecomprising an olefin, a metal alkyl, and a second solvent; c) contactingthe composition formed in step a) and the mixture formed in step b); andd) forming an olefin oligomer product. In an embodiment, the olefinpolymerization process can comprise: a) forming a compositioncomprising, or consisting essentially of, an N²-phosphinyl amidinecompound, a metal salt, and a first solvent; b) forming a mixturecomprising an olefin, a metal alkyl, and a second solvent; c) contactingthe composition formed in step a) and the mixture formed in step b); andd) forming an olefin polymer product. In some embodiments, the first andsecond solvent can be the same; or alternatively, the first and secondsolvent can be different. The N²-phosphinyl amidine compound, metalsalt, metal alkyl, olefin, solvents, and features of the olefin oligomeror olefin polymer product (among other catalyst system and olefinoligomerization or polymerization features) are independently describedherein and can be utilized, without limitation to further describe theolefin oligomerization or olefin polymerization process. In someembodiments, the metal alkyl can comprise an aluminoxane. Ratios for theN²-phosphinyl amidine compound to metal salt and ratios for the metal ofthe metal alkyl to metal of the metal salt are independently providedherein (among other catalyst system and olefin oligomerization orpolymerization features) and can be utilized without limitation tofurther describe the olefin oligomerization or olefin polymerizationprocess.

In an embodiment, a solvent utilized with the catalyst system, a mixturecomprising an N²-phosphinyl amidine metal salt complex, a mixturecomprising an N²-phosphinyl amidine metal salt complex and a metalalkyl, a composition comprising an N²-phosphinyl amidine compound and ametal salt, or a composition comprising an N²-phosphinyl amidinecompound, a metal salt, and a metal alkyl can be a hydrocarbon solvent,a halogenated hydrocarbon solvent, or any combination thereof;alternatively, a hydrocarbon solvent; or alternatively, a halogenatedhydrocarbon solvent. In some embodiments, a solvent utilized with amixture comprising an N²-phosphinyl amidine metal salt complex, amixture comprising an N²-phosphinyl amidine metal salt complex and ametal alkyl, a composition comprising an N²-phosphinyl amidine compoundand a metal salt, or a composition comprising an N²-phosphinyl amidinecompound, a metal salt, and a metal alkyl can be an aliphatichydrocarbon solvent, a halogenated aliphatic hydrocarbon solvent, anaromatic hydrocarbon solvent, a halogenated aromatic solvent, or anycombination thereof; alternatively, an aliphatic hydrocarbon solvent, ahalogenated aliphatic hydrocarbon solvent, or any combination thereof;alternatively, an aromatic hydrocarbon solvent, a halogenated aromaticsolvent, or any combination thereof; alternatively, an aliphatichydrocarbon solvent; alternatively, a halogenated aliphatic hydrocarbonsolvent; alternatively, an aromatic hydrocarbon solvent; oralternatively, a halogenated aromatic solvent. General and specifichydrocarbon solvents, halogenated hydrocarbon solvents, aliphatichydrocarbon solvents, halogenated aliphatic hydrocarbon solvents,aromatic hydrocarbon solvents, and halogenated aromatic solvents aredescribed herein and can be utilized without limitation to furtherdescribe the olefin oligomerization or olefin polymerization process(es)described herein.

In an embodiment, a solvent utilized in any mixture including the olefinor utilized to form the olefin product or polymer product can behydrocarbon solvent, a halogenated hydrocarbon solvent, or anycombination thereof; alternatively, a hydrocarbon solvent; oralternatively, a halogenated hydrocarbon solvent. In some embodiments, asolvent utilized in any mixture including the olefin or utilized to formthe olefin product or polymer product can be an aliphatic hydrocarbonsolvent, a halogenated aliphatic hydrocarbon solvent, an aromatichydrocarbon solvent, a halogenated aromatic solvent, or any combinationthereof; alternatively, an aliphatic hydrocarbon solvent, a halogenatedaliphatic hydrocarbon solvent, or any combination thereof;alternatively, an aromatic hydrocarbon solvent, a halogenated aromaticsolvent, or any combination thereof; alternatively, an aliphatichydrocarbon solvent; alternatively, a halogenated aliphatic hydrocarbonsolvent; alternatively, an aromatic hydrocarbon solvent; oralternatively, a halogenated aromatic solvent. General and specifichydrocarbon solvents, halogenated hydrocarbon solvents, aliphatichydrocarbon solvents, halogenated aliphatic hydrocarbon solvents,aromatic hydrocarbon solvents, and halogenated aromatic solvents aredescribed herein and can be utilized without limitation to furtherdescribe the olefin oligomerization or olefin polymerization processdescribed herein.

In some embodiments, the solvent utilized with the catalyst system, amixture comprising an N²-phosphinyl amidine metal salt complex, amixture comprising an N²-phosphinyl amidine metal salt complex and ametal alkyl, a composition comprising an N²-phosphinyl amidine compoundand a metal salt, or a composition comprising an N²-phosphinyl amidinecompound, a metal salt, and a metal alkyl and the solvent utilized inany mixture including the olefin or utilized to form the olefin oligomerproduct or olefin polymer product can be the same; or alternatively, canbe different. In an embodiment, the solvent utilized with the catalystsystem, a mixture comprising an N²-phosphinyl amidine metal saltcomplex, a mixture comprising an N²-phosphinyl amidine metal saltcomplex and a metal alkyl, a composition comprising an N²-phosphinylamidine compound and a metal salt, or a composition comprising anN²-phosphinyl amidine compound, a metal salt, and a metal alkyl and thesolvent utilized in any mixture including the olefin or utilized to formthe olefin product or product has a boiling point which allows for itseasy separation (e.g. by distillation) from the olefin oligomer productor olefin polymer product.

Generally, the olefin which can be oligomerized or polymerized cancomprise, or consist essentially of, a C₂ to C₃₀ olefin; alternatively,a C₂ to C₁₆ olefin; or alternatively, a C₂ to C₁₀ olefin. In anembodiment, the olefin can be an alpha olefin; alternatively, a linearalpha olefin; or alternatively, a normal alpha olefin. In an embodiment,the olefin can comprise, or consist essentially of, ethylene, propylene,or a combination thereof; alternatively, ethylene; or alternatively,propylene. When the olefin consists essentially of ethylene, the olefinoligomerization process can be an ethylene oligomerization process or anethylene polymerization process.

In an aspect, the olefin oligomerization process can be an olefintrimerization process; alternatively, an olefin tetramerization process;or alternatively, an olefin trimerization and tetramerization process.When the olefin is ethylene, the olefin oligomerization process can bean ethylene trimerization process; alternatively, an ethylenetetramerization process; or alternatively, an ethylene trimerization andtetramerization process. When the process is an ethylene trimerizationprocess, the olefin product can comprise hexene; or alternatively, cancomprise 1-hexene. When the process is an ethylene tetramerizationprocess, the olefin product can comprise octene; or alternatively, cancomprise 1-octene. When the process is an ethylene trimerization andtetramerization process, the olefin product can comprise hexene andoctene; or can comprise 1-hexene and 1-octene.

Unless otherwise specified, the terms contacted, combined, and “in thepresence of” refer to any addition sequence, order, or concentration forcontacting or combining two or more components of the oligomerizationprocess. Combining or contacting of oligomerization components,according to the various methods described herein can occur in one ormore contact zones under suitable contact conditions such astemperature, pressure, contact time, flow rates, etc. . . . The contactzone can be disposed in a vessel (e.g. a storage tank, tote, container,mixing vessel, reactor, etc.), a length of pipe (e.g. a tee, inlet,injection port, or header for combining component feed lines into acommon line), or any other suitable apparatus for bringing thecomponents into contact. The processes can be carried out in a batch orcontinuous process as is suitable for a given embodiment.

In an embodiment, the olefin oligomerization or olefin polymerizationcan be a continuous process carried out in one or more reactors. In someembodiments, the continuous olefin oligomerization or olefinpolymerization reactor can comprise a loop reactor, a tubular reactor, acontinuous stirred tank reactor (CSTR), or combinations thereof. Inother embodiments, the continuous olefin oligomerization or olefinpolymerization reactor can be a loop reactor; alternatively, a tubularreactor; or alternatively, a continuous stirred tank reactor (CSTR). Inother embodiments, the continuous olefin oligomerization or olefinpolymerization reactor can be employed in the form of different types ofcontinuous reactors in combination, and in various arrangements.

In an embodiment, the olefin product or polymer product can be formedunder suitable oligomerization or polymerization reaction conditionssuch as reaction temperatures, reaction pressure, and/or reaction times.Reaction temperatures, reaction pressure, and/or reaction times can beimpacted by a number of factors such as the metal complex stability,metal complex activity, cocatalyst identity, cocatalyst activity,desired product distribution, and/or desired product purity among otherfactors.

Generally, the olefin oligomerization or olefin polymerization can beperformed using any N²-phosphinyl amidine compound, metal salt, orN²-phosphinyl amidine metal complex concentration that forms the desiredolefin product or olefin polymer. In an embodiment, the concentration ofthe N²-phosphinyl amidine compound, metal salt, or N²-phosphinyl amidinemetal complex can be at least 1×10⁻⁶ equivalents/liter; alternatively,at least 1×10⁻⁵ equivalents/liter; or alternatively, at least 5×10⁻⁴equivalents/liter. In other embodiments, the concentration of thediphosphino aminyl complexed metal compound can range from 1×10⁻⁶equivalents/liter to 1 equivalents/liter; alternatively, range from1×10⁻⁵ equivalents/liter to 5×10⁻¹ equivalents/liter; or alternatively,range from 5×10⁴ equivalents/liter to 1×10⁻¹ equivalents/liter.

Generally, the olefin oligomerization or olefin polymerization reactionpressure can be any pressure that facilitates the oligomerization orpolymerization of the olefin. In an embodiment, the reaction pressure ofthe olefin oligomerization or olefin polymerization process can be anyreaction pressure required to produce the desired olefin product orpolymer product. In some embodiments, the olefin oligomerization orolefin polymerization pressure can be greater than or equal to 0 psig (0KPa); alternatively, greater than or equal to 50 psig (344 KPa);alternatively, greater than or equal to 100 psig (689 KPa); oralternatively, greater than or equal to 150 psig (1.0 MPa). In otherembodiments, the olefin oligomerization or olefin polymerizationpressure can range from 0 psig (0 KPa) to 5,000 psig (34.5 MPa);alternatively, 50 psig (344 KPa) to 4,000 psig (27.6 MPa);alternatively, 100 psig (689 KPa) to 3,000 psig (20.9 MPa); oralternatively, 150 psig (1.0 MPa) to 2,000 psig (13.8 MPa). Inembodiments wherein the monomer is a gas (e.g. ethylene), the olefinoligomerization or olefin polymerization pressure can be carried outunder a monomer gas pressure. When the olefin oligomerization or olefinpolymerization pressure produces an ethylene oligomer or polyethylene,the reaction pressure can be the monomer ethylene pressure. In someembodiments, the ethylene pressure can be greater than or equal to 0psig (0 KPa); alternatively, greater than or equal to 50 psig (344 KPa);alternatively, greater than or equal to 100 psig (689 KPa); oralternatively, greater than or equal to 150 psig (1.0 MPa). In otherembodiments, the ethylene pressure can range from 0 psig (0 KPa) to5,000 psig (34.5 MPa); alternatively, 50 psig (344 KPa) to 4,000 psig(27.6 MPa); alternatively, 100 psig (689 KPa) to 3,000 psig (20.9 MPa);or alternatively, 150 psig (1.0 MPa) to 2,000 psig (13.8 MPa). In somecases when ethylene is the monomer, inert gases can form a portion ofthe total reaction pressure. In the cases where inert gases form aportion of the reaction pressure, the previously stated ethylenepressures can be the applicable ethylene partial pressures of thepolymerization or oligomerization reaction. In the situation where themonomer provides all or a portion of the olefin oligomerization orolefin polymerization pressure, the reaction system pressure candecrease as the gaseous monomer is consumed. In this situation,additional gaseous monomer and/or inert gas can be added to maintain adesired olefin oligomerization or olefin polymerization pressure. Insome embodiments, additional gaseous monomer can be added to the olefinoligomerization or olefin polymerization pressure at a set rate (e.g.for a continuous flow reactor), or at different rates (e.g. to maintaina set system pressure in a batch reactor). In other embodiments, theolefin oligomerization or olefin polymerization pressure can be allowedto decrease without adding any additional gaseous monomer and/or inertgas.

In embodiments wherein hydrogen is utilized, hydrogen can be added inany amount that produces the desired effect. In some embodiments, thehydrogen partial pressure can be greater than or equal to 1 psig (kPa);alternatively, greater than or equal to 5 psig (34 kPa); alternatively,greater than or equal to 10 psig (69 kPa); or alternatively, greaterthan or equal to 15 psig (100 kPa). In other embodiments, the hydrogenpartial pressure can range from 1 psig (6.9 kPa) to 500 psig (3.5 MPa);alternatively, 5 psig (34 kPa) to 400 psig (2.8 MPa); alternatively, 10psig (69 kPa) to 300 psig (2.1 MPa); or alternatively, 15 psig (100 kPa)to 200 psig (1.4 MPa).

In an embodiment, a condition to form an olefin product or polymerproduct can include an oligomerization temperature or polymerizationtemperature. Generally, the oligomerization temperature orpolymerization temperature can be any temperature which forms thedesired olefin product or polymer product. In an embodiment, theoligomerization temperature or polymerization temperature can be atleast 0° C.; alternatively, at least 10° C.; alternatively, at least 20°C.; or alternatively, at least 30° C. In some embodiments, theoligomerization temperature or polymerization temperature can range from0° C. to 200° C.; alternatively, range from 10° C. to 160° C.;alternatively, ranges from 20° C. to 140° C.; or alternatively, rangesfrom 30° C. to 120° C.

In an embodiment, a condition to form an olefin product or polymerproduct can include an oligomerization time or polymerization time.Generally, the oligomerization time or polymerization time can be anytime that produces the desired quantity of olefin product or polymerproduct; or alternatively, provide a desired catalyst systemproductivity; or alternatively, provide a desired conversion of monomer.In some embodiments, the oligomerization time or polymerization time canrange from 1 minute to 5 hours; alternatively, ranges from 5 minutes to2.5 hours; alternatively, ranges from 10 minutes to 2 hours; oralternatively, ranges from 15 minutes to 1.5 hours. In an embodiment,the olefin oligomerization can have a single pass olefin conversion ofethylene of at least 30 wt. % percent; alternatively, at least 35 wt. %percent; alternatively, at least 40 wt. % percent; or alternatively, atleast 45 wt. % percent. When the olefin is ethylene, the olefinconversion is ethylene conversion.

In an embodiment, the olefin oligomerization process produces an olefinproduct comprising an olefin trimer, an olefin tetramer, or mixturesthereof. In some embodiments, when the olefin is ethylene the olefinoligomerization is an ethylene oligomerization process. In someembodiments, the olefin oligomerization produces an alpha olefin producthaving at least four carbon atoms. In an embodiment, the ethyleneoligomerization process produces an olefin product comprising anethylene trimer (e.g. hexene, or alternatively, 1-hexene), an ethylenetetramer (e.g. octene, or alternatively, 1-octene), or a combinationthereof; alternatively, hexene; alternatively, octene; alternatively,hexene and octene. In other embodiments, the ethylene oligomerizationproduces an olefin product comprising 1-hexene, 1-octene, or acombination thereof; alternatively, 1-hexene; alternatively, 1-octene;alternatively, 1-hexene and 1-octene. In an embodiment, when the olefinis ethylene and the process produces an alpha olefin (e.g. 1-hexene,1-octene, or a combination thereof) the olefin oligomerization processcan be an alpha olefin production process.

In an embodiment, the ethylene oligomerization process can produce anolefin product comprising a liquid product comprising at least 60 wt. %C₆ and C_(s) olefins. In some embodiments, the olefin product comprisesa liquid product comprising at least 70 wt. % C₆ and C_(s) olefins;alternatively, at least 75 wt. % C₆ and C_(s) olefins; alternatively, atleast 80 wt. % C₆ and C_(s) olefins; alternatively, at least 85 wt. % C₆and C_(s) olefins; or alternatively, at least 90 wt. % C₆ and C_(s)olefins. In other embodiments, the ethylene oligomerization process canproduce an olefin product comprising a liquid product having from 60 to99.9 wt. % of C₆ and C_(s) olefins; alternatively, from 70 to 99.8 wt. %C₆ and C_(s) olefins; alternatively, from 75 to 99.7 wt. % C₆ and C_(s)olefins; or alternatively, from 80 to 99.6 wt. % C₆ and C_(s) olefins.Throughout this application, a liquid product refers to the olefinoligomer product having from 4 to 18 carbon atoms.

In an embodiment, the ethylene oligomerization process can produce anolefin product comprising a liquid product comprising at least 60 wt. %C₆ olefins. In some embodiments, the olefin product can comprise aliquid product comprising at least 70 wt. % C₆ olefins; alternatively,at least 75 wt. % C₆ olefins; alternatively, at least 80 wt. % C₆olefins; alternatively, at least 85 wt. % C₆ olefins; or alternatively,at least 90 wt. % C₆ olefins. In other embodiments, the ethyleneoligomerization process can produce an olefin product comprising aliquid product having from 60 to 99.9 wt. % of C₆ olefins;alternatively, from 70 to 99.8 wt. % C₆ olefins; alternatively, from 75to 99.7 wt. % C₆ olefins; or alternatively, from 80 to 99.6 wt. % C₆olefins; or alternatively, 85 to 99.6 wt. % C₆ olefins.

In an embodiment, the C₆ olefin product produced by the ethyleneoligomerization process can comprise at least 85 wt. % 1-hexene. In someembodiments, the C₆ olefin product produced by the ethyleneoligomerization process can comprise at least 87.5 wt. % 1-hexene;alternatively, at least 90 wt % 1-hexene; alternatively, at least 92.5wt. % 1-hexene; alternatively, at least 95 wt. percent 1-hexene;alternatively, at least 97 weight percent 1-hexene; or alternatively, atleast 98 weight percent 1-hexene. In other embodiments, the C₆ olefinproduct produced by the ethylene oligomerization process can comprisefrom 85 to 99.9 wt % 1-hexene; alternatively, from 87.5 to 99.9 wt %1-hexene; alternatively, from 90 to 99.9 wt % 1-hexene; alternatively,from 92.5 to 99.9 wt % 1-hexene; alternatively, from 95 to 99.9 wt. %1-hexene; alternatively, from 97 to 99.9 wt. % 1-hexene; oralternatively, from 98 to 99.9 wt. % 1-hexene.

In an embodiment, the C_(s) olefin product produced by the ethyleneoligomerization process can comprise at least 85 wt. % 1-octene. In someembodiments, the C_(s) olefin product produced by the ethyleneoligomerization process can comprise at least 87.5 wt. % 1-octene;alternatively, at least 90 wt % 1-octene; alternatively, at least 92.5wt. % 1-octene; alternatively, at least 95 wt. percent 1-octene;alternatively, at least 97 weight percent 1-octene; or alternatively, atleast 98 weight percent 1-octene. In other embodiments, the C_(s) olefinproduct produced by the ethylene oligomerization process can comprisefrom 85 to 99.9 wt % 1-octene; alternatively, from 87.5 to 99.9 wt %1-octene; alternatively, from 90 to 99.9 wt % 1-octene; alternatively,from 92.5 to 99.9 wt % 1-octene; alternatively, from 95 to 99.9 wt. %1-octene; alternatively, from 97 to 99.9 wt. % 1-octene; oralternatively, from 98 to 99.9 wt. % 1-octene.

It has been discovered that, in some aspects and/or embodiments, agingthe catalyst system before contacting the catalyst system with theolefin to be oligomerized and/or polymerized can improve aspects of theolefin oligomerization and/or olefin polymerization process. Firstly, ithas been observed that aging the catalyst system can increase theproductivity of the catalyst system. Secondly, in olefinoligomerization, it has been observed that aging the catalyst system candecrease the amount of polymer produced in an olefin oligomerizationprocess. In some olefin oligomerization aspects and/or embodiments,aging the catalyst system can increase the productivity of the catalystsystem; alternatively, can decrease the amount of polymer produced inthe olefin oligomerization; or alternatively, can increase theproductivity of the catalyst system and decrease the amount of polymerproduced in the olefin oligomerization.

The catalyst system aging impacts can be utilized to provide positivebenefits to olefin oligomerization and/or olefin polymerizationprocesses. For example, increasing the activity and/or the productivityof the catalyst system can provide increased olefin oligomer product perunit of catalyst system among other benefits. Additionally, the decreasein polymer produced in an olefin oligomerization upon aging the catalystsystem can reduce polymer which could adhere to the oligomerizationreactor walls or cooling apparatus. The reduction in polymer produced inthe olefin oligomerization process can reduce the need to shut down areactor to remove the polymer which can cause fouling.

In any aspect or embodiment wherein an N²-phosphinyl amidine compound, ametal salt, and a metal alkyl are contacted prior to contacting theolefin, the mixture comprising the N²-phosphinyl amidine compound, themetal salt, and the metal alkyl can be allowed to age for a period oftime prior to contacting the mixture comprising the N²-phosphinylamidine compound, a metal salt, and a metal alkyl with a mixturecomprising the olefin. In some embodiments, a mixture comprising anN²-phosphinyl amidine compound, a metal salt, and a metal alkyl canfurther comprise a solvent.

In any aspect or embodiment wherein an N²-phosphinyl amidine metal saltcomplex and a metal alkyl are contacted prior to contacting the olefin,the mixture comprising the N²-phosphinyl amidine metal salt complex andthe metal alkyl can be allowed to age for a period of time prior tocontacting the mixture comprising the N²-phosphinyl amidine metal saltcomplex and the metal alkyl with a mixture comprising the olefin. Insome embodiments, a mixture comprising an N²-phosphinyl amidine metalsalt complex and a metal alkyl can further comprise a solvent.

In a non-limiting embodiment, the olefin oligomerization process cancomprise: a) preparing a catalyst system; b) allowing the catalystsystem to age for a period of time; c) contacting the aged catalystsystem with an olefin; and d) forming an olefin oligomer product. Insome non-limiting embodiments, the olefin oligomerization process cancomprise, a) preparing a catalyst system; b) allowing the catalystsystem to age for a period of time; c) contacting the aged catalystsystem with an olefin and hydrogen; and d) forming an olefin oligomerproduct. The catalyst system, olefin, and other features of the olefinoligomerization and olefin polymer product are independently describedherein and can be utilized, without limitation to further describe theolefin oligomerization process. In some embodiments, the catalyst systemcan be prepared in a first solvent. In an embodiment, the olefin, agedcatalyst system, and optionally hydrogen, can be contacted in a secondsolvent. Generally, a solvent in which the catalyst system can beprepared and the solvent in which the olefin and aged catalyst systemcan be contacted can be the same; or alternatively, can be different.The catalyst system, features of aging the catalyst system, features ofthe olefin oligomer, and features of the impacts of aging the catalystssystem, among other features, are independently described herein and canbe utilized, without limitation to further describe the olefinoligomerization process. In some embodiments, the first and secondsolvent can be the same; or alternatively, the first and second solventcan be different.

In a non-limiting embodiment, the olefin oligomerization process cancomprise: a) forming a catalyst system mixture comprising anN²-phosphinyl amidine metal salt complex and metal alkyl; b) aging thecatalyst system mixture; c) contacting the aged catalyst system mixturewith an olefin; and c) forming an olefin oligomer product. In anothernon-limiting embodiment, the olefin oligomerization process cancomprise: a) forming a catalyst system mixture comprising anN²-phosphinyl amidine compound, a metal salt, and a metal alkyl; b)aging the catalyst system mixture; c) contacting the aged catalystsystem mixture with an olefin; and c) forming an olefin oligomerproduct. In some embodiments the catalyst system mixture can furthercomprise a solvent (e.g. a first solvent). In some embodiments, thecatalyst system mixture and the olefin can be contacted in a solvent(e.g. a second solvent). In yet another non-limiting embodiment, theolefin oligomerization process can comprise: a) forming a catalystsystem mixture comprising (or consisting essentially of) anN²-phosphinyl amidine metal salt complex, a metal alkyl, and a firstsolvent; b) aging the catalyst system mixture; c) contacting the agedcatalyst system mixture with an olefin and a second solvent; and c)forming an olefin oligomer product. In a further non-limitingembodiment, the olefin oligomerization process can comprise: a) forminga catalyst system mixture comprising (or consisting essentially of) anN²-phosphinyl amidine compound, a metal salt, a metal alkyl, and a firstsolvent; b) aging the catalyst system mixture; c) contacting the agedcatalyst system mixture with an olefin and a second solvent; and d)forming an olefin oligomer product.

In some embodiments, the step of contacting the aged catalyst systemmixture with the olefin (and optionally a solvent—e.g. second solvent)can be a step of contacting the aged catalyst system mixture with anolefin and hydrogen. The N²-phosphinyl amidine compound, metal salt, themetal salt N²-phosphinyl amidine metal salt complex, the metal alkyl,the olefin, solvents, features of aging the catalyst system, features ofthe olefin oligomer, and features of the impacts of aging the catalystssystem, among other features, are independently described herein and canbe utilized, without limitation to further describe the olefinoligomerization. In some embodiments, the first and second solvent canbe the same; or alternatively, the first and second solvent can bedifferent. In some embodiments, the metal alkyl can comprise analuminoxane. Ratios for the N²-phosphinyl amidine compound to metal saltand ratios for the metal of the metal alkyl to metal of the metal saltor the metal of the N²-phosphinyl amidine metal salt complex, amongother features, are independently described herein and can be utilizedwithout limitation to further describe the olefin oligomerization orolefin polymerization process.

In an embodiment, the catalyst system can be aged for up 14 days;alternatively, up to 10 days; alternatively, up to 8 days;alternatively, up to 6 days; alternatively, up to 4 days; alternatively,up to 3 days; alternatively, up to 48 hours; alternatively, up to 36hours; alternatively, up to 24 hours; alternatively, up to 18 hours;alternatively, up to 10 hours; alternatively, up to 8 hours;alternatively, up to 6 hours; alternatively, up to 4 hours; oralternatively, up to 3 hours. In an embodiment, the catalyst system canbe aged for at least 15 minutes; alternatively, at least 20 minutes; oralternatively, at least 30 minutes. In an embodiment, the catalystsystem can be aged for a time ranging from any catalyst system agingminimum time disclosed herein to any catalyst system aging maximum timedisclosed herein. In some non-limiting embodiments, the catalyst systemcan be aged for from 15 minutes to 14 days; alternatively, from 15minutes to 10 days; alternatively, from 15 minutes to 8 days;alternatively, from 15 minutes to 6 days; alternatively, from 20 minutesto 4 days; alternatively, from 20 minutes to 3 days; alternatively, from30 minutes to 48 hours; alternatively, from 30 minutes to 36 hours;alternatively, from 30 minutes to 24 hours; alternatively, from 30minutes to 18 hours; alternatively, from 30 minutes to 10 hours;alternatively, from 30 minutes to 8 hours; alternatively, from 30minutes to 6 hours; alternatively, from 30 minutes to 4 hours; oralternatively, from 30 minutes to 3 hours.

In an embodiment, any catalyst system described herein can be aged atambient temperature (15° C.-35° C.—no external heat source). In otherembodiments, any catalyst system described herein can be aged at atemperature from 25° C. to 100° C.; alternatively, from 30° C. to 80°C.; or alternatively, from 35° C. to 60° C. In some embodiments, anycatalyst system described herein can be aged under an inert atmosphere.Generally, one can recognize that the temperature at which the catalystsystem is aged can have an impact upon the time necessary to achieve anincrease in catalyst system activity and/or reduction in catalyst systempolymer production. In any aspect or embodiment, the catalyst system canbe aged at a combination of any catalyst system aging time describedherein and any aging catalyst system aging temperature described herein.

The catalytic activity of any olefin oligomerization or polymerizationcatalyst system described herein comprising any N²-phosphinyl amidinemetal salt complex or comprising any N²-phosphinyl amidine compounddescribed herein and any metal salt described herein can be defined asthe grams of product produced per gram of metal of the metal salt in theN²-phosphinyl amidine metal salt complex utilized and is measured over30 minutes beginning from when complete catalyst system is contactedwith the olefin. In an embodiment, any aged catalyst system describedherein (using any aging time period described herein and/or any agingtemperature described herein) can increase the olefin oligomerization orolefin polymerization activity of the catalyst system by at least 10%;alternatively, at least 20%; alternatively, at least 30%; alternatively,at least 40%; or alternatively, at least 50%. In some embodiments, anyaged catalyst system described herein (using any aging time perioddescribed herein and/or any aging temperature described herein) canincrease the olefin oligomerization or olefin polymerization activity ofthe catalyst system from 10 to 1000%; alternatively, from 20 to 800%;alternatively, from 30 to 600%; alternatively, from 40 to 500%; oralternatively, from 50 to 400%. Generally, the increase in the olefinoligomerization or olefin polymerization catalyst system activity as aresult of aging the catalyst system is determined by comparing theactivity of the aged catalyst system to the activity of a catalystsystem that has been aged for less than 12 minutes.

In an embodiment, any aged catalyst system described herein (using anyaging time period described herein and/or any aging temperaturedescribed herein) can provide a catalyst system which can produce areduction in the percentage of polymer produced described herein. Insome embodiments, aging of any catalyst system described herein canreduce (using any aging time period described herein and/or any agingtemperature described herein) the amount of polymer produced in anolefin oligomerization process by at least 5%; alternatively, 7.5%;alternatively, 10%; alternatively, 12.5%; or alternatively, at least15%. In some embodiments, aging of any catalyst system described herein(for any time period described herein) can reduce the amount of polymerproduced in an olefin oligomerization by at least 20%; alternatively, atleast 25%; alternatively, at least 30%; or alternatively, at least 35%.Generally, the decrease in the catalyst system polymer production as aresult of aging can be determined by comparing the polymer production ofthe aged catalyst system to the polymer production of a catalyst systemthat has been aged for less than 12 minutes.

In an embodiment, aging any olefin oligomerization catalyst systemdescribed herein can have a combination of any increase in activitydescribed herein and any reduction in the amount of polymer produceddescribed herein.

In an embodiment, a calibration curve can be produced depicting thecatalyst system activity and/or polymer production of any aged catalystsystem described herein in response to one or more catalyst system agingvariables (e.g. time, temperature, or time and temperature). In someembodiments the calibration curve can be depicted graphically as afunction of a catalyst system aging variable(s) (e.g. time, temperature,or time and temperature); or alternatively, the calibration curve can bedepicted as a predictive equation of a catalyst system aging variable(s)(e.g. time, temperature, or time and temperature). The graphicalrepresentation and/or predictive equation relating catalyst systemactivity and/or polymer production in response catalyst aging can beutilized to adjust one or more user and/or process parameters based uponthe interpolation or extrapolation of the graphical representation orpredictive equation. It is contemplated that in some aspects, the extentto which the catalyst system activity increases and/or the extent towhich there is a decrease in polymer production with respect to catalystsystem aging can fall outside the instantly disclosed ranges and can belarger than would be expected based on the presently disclosed valuesdepending on conditions under which the catalyst system is aged. Forexample, the catalyst system can be subjected to aging for time periodsthat are longer than those presently recited and/or at temperaturesgreater than those presently recited. The effects of aging the catalystsystem under such conditions can be subject to the herein mentionedanalysis to provide predictive information that can lead one toconditions under which catalyst system aging increases the catalystsystem activity and/or reduces the polymer production in the olefinoligomerization to within some user and/or process desired range ofvalues. It is contemplated that given the benefits of this disclosureand using routine experimentation one having ordinary skill in the artcan modify the methodologies disclosed herein to alter the catalyticsystem activity of a disclosed catalyst system and/or reduce the amountof polymer produced in an olefin oligomerization process to a desiredvalue or range. Such modifications fall within the scope of thisdisclosure.

It has also been discovered that when the metal alkyl is an alumoxane(also referred to as an aluminoxane), aging the alumoxane can improveaspects of the olefin oligomerization. For example, it has been observedthat aging the alumoxane prior to its contact with the other componentsof the catalyst system can decrease the amount of polymer produced inthe olefin oligomerization process. In some embodiments, any process forpreparing the catalyst system described herein and/or any olefinoligomerization process described herein can include a step (or steps)for aging an alumoxane.

In an embodiment, the alumoxane can be aged at ambient temperature (15°C.-35° C.—no external heat source) for at least 2 months; at least 4months; at least 6 months; or at least 8 months. In some embodiments,the alumoxane can be aged at ambient temperature (15° C.-35° C.—noexternal heat source) from 2 months to 4 years; from 4 months to 3years; from 6 months to 2.5 years; or from 8 months to 2 years. In someembodiments, the alumoxane can be aged under an inert atmosphere.

The aging of the alumoxane can be performed at elevated temperature. Ithas been discovered that the aging of the alumoxane at elevatedtemperature can reduce the time needed to achieve the benefits observedwhen the aged alumoxane is utilized in an olefin oligomerizationcatalyst system. In an embodiment, the alumoxane can be aged at atemperature from 30° C. to 100° C.; from 35° C. to 90° C.; from 40° C.to 80° C.; or 45° C. to 70° C. In an embodiment, the alumoxane can beaged at any elevated temperature disclosed herein for at least 12 hours;at least 18 hours; at least 24 hours; or at least 36 hours. In anembodiment, the alumoxane can be aged at any elevated temperaturedisclosed herein for up to 1 year; up to 9 months; up to 6 months; or upto 3 months. In some embodiments, the alumoxane can be aged under aninert atmosphere. In an embodiment, the alumoxane can be aged for a timeranging from any alumoxane aging minimum time disclosed herein to anyalumoxane aging maximum time disclosed herein. In some embodiments, thealumoxane can be aged at any elevated temperature disclosed herein andany alumoxane aging time disclosed herein.

In an embodiment, any aging of the alumoxane described herein canprovide any reduction in the percentage of polymer produced by theolefin oligomerization described herein. In some embodiments, any agingof the alumoxane described herein can reduce the amount of polymerproduced in an olefin oligomerization process by at least 20%; at least40%; at least 60%; at least 70%; at least 75%; at least 80%; or at least85%.

In an embodiment, a calibration curve can be produced depicting thepolymer production of any catalyst system described herein utilizing anaged alumoxane in response to one or more alumoxane aging variables(e.g. time, temperature, or time and temperature). In some embodimentsthe alumoxane aging calibration curve can be depicted graphically as afunction of an alumoxane aging variable(s) (e.g. time, temperature, ortime and temperature); alternatively, the calibration curve can bedepicted as a predictive equation of an alumoxane aging variable(s)(e.g. time, temperature, or time and temperature). The graphicalrepresentation and/or predictive equation relating catalyst systempolymer production in response to alumoxane aging can be utilized toadjust one or more user and/or process parameters based upon theinterpolation or extrapolation of the graphical representation orpredictive equation. It is contemplated that in some aspects, the extentto which the polymer production of the catalyst system decreases withrespect to alumoxane aging can fall outside the instantly disclosedranges and can be larger than would be expected based on the presentlydisclosed values depending on the conditions under which alumoxane isaged. For example, the catalyst system can be subjected to aging fortime periods that are longer than those presently recited and/or attemperatures greater than those presently recited. The effects ofalumoxane aging under such conditions can be subject to the hereinmentioned analysis to provide predictive information that can lead toconditions under which alumoxane aging can reduce the polymer productionof the catalyst system in the olefin oligomerization. It is contemplatedthat given the benefits of this disclosure and using routineexperimentation one having ordinary skill in the art can modify themethodologies disclosed herein to alter a reduction in the amount ofpolymer produced in an olefin oligomerization. Such modifications fallwithin the scope of this disclosure.

Within this disclosure, amines can be used to ultimately prepare theN²-phosphinyl amidine compounds and/or the N²-phosphinyl amidine metalsalt complexes utilized in various aspects of this disclosure. Invarious embodiments, amines which can be utilized have Structure A1-A5;alternatively, A1; alternatively, A2; alternatively, A3; alternatively,A4; or alternatively, A5.

R¹—NH₂ H₂N—L¹—NH₂ D¹ NH₂)_(q) Structure A1 Structure A2 Structure A3Q¹—L³—NH₂ R³—NH₂ Structure A4 Structure A5R¹, R³, D¹, L¹, L³, Q¹, and q within amine Structures A1-A5 areindependently described as features of the N²-phospinyl amidinecompounds Structures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and/orNP20. Since amines having Structures A1-A4 are ultimately utilized toprepare embodiments of N²-phospinyl amidine compounds having StructuresNP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20, the R¹, R³, D¹, L¹,L³, Q¹, and q descriptions for the N²-phospinyl amidine compounds can beutilized without limitation to further describe the amine StructuresA1-A5.

In an aspect, the amine having Structure A1 or Structure A5 can bemethylamine, ethylamine, a propylamine, a butylamine, a pentylamine, ahexylamine, a heptylamine, an octylamine, a nonylamine, a decylamine, aundecylamine, a dodecylamine, a tridecylamine, a tetradecylamine, apentadecylamine, a hexadecylamine, a heptadecylamine, an octadecylamine,or a nonadecylamine; or alternatively, methylamine, ethylamine, apropylamine, a butylamine, a pentylamine, a hexylamine, a heptylamine,an octylamine, a nonylamine, or a decylamine. In some embodiments, theamine having Structure A1 or Structure A5 can be methylamine,ethylamine, n-propylamine, iso-propylamine, butylamine, iso-butylamine,sec-butylamine, tert-butylamine, n-pentylamine, iso-pentylamine,sec-pentylamine, or neopentylamine; alternatively, methylamine,ethylamine, iso-propylamine, tert-butylamine, or neopentylamine;alternatively, methylamine; alternatively, ethylamine; alternatively,n-propylamine; alternatively, iso-propylamine; alternatively,tert-butylamine; or alternatively, neopentylamine.

In other aspects, the amine having Structure A1 or Structure A5 can becyclobutylamine, a substituted cyclobutylamine, cyclopentylamine, asubstituted cyclopentylamine, cyclohexylamine, a substitutedcyclohexylamine, cycloheptylamine, a substituted cycloheptylamine,cyclooctylamine, or a substituted cyclooctylamine. In an embodiment theamine having Structure A1 or Structure A5 can be cyclopentylamine, asubstituted cyclopentylamine, cyclohexylamine, or a substitutedcyclohexylamine. In other embodiments, the amine having Structure A1 orStructure A5 can be cyclobutylamine or a substituted cyclobutylamine;alternatively, a cyclopentylamine or a substituted cyclopentylamine;alternatively, a cyclohexylamine or a substituted cyclohexylamine;alternatively, a cycloheptylamine or a substituted cycloheptylamine; oralternatively, a cyclooctylamine, or a substituted cyclooctylamine. Infurther embodiments, the amine having Structure A1 or Structure A5 canbe cyclopentylamine; alternatively, a substituted cyclopentylamine; acyclohexylamine; or alternatively, a substituted cyclohexylamine.Substituents and substituents patterns for the R¹ and R³ cycloalkylgroups are described herein and can be utilized without limitation tofurther describe the substituted cycloalkylamines which can be utilizedas the amine having Structure A1 or Structure A5 in aspects and/orembodiments described herein.

In an aspect, the amine having Structure A1 can have Structure A6. In anaspect, the amine having Structure A5 can have Structure A7.

The R^(11c), R^(12c), R^(13c), R^(14c), and R^(15c) substituents,substituent patterns, and n for the R¹ group having Structure G1 aredescribed herein and can be utilized without limitation to describe theamine having Structure A6 which can be utilized in the various aspectsand embodiments described herein. The R^(31c), R^(32c), R^(33c),R^(34c), and R^(35c) substituents, substituent patterns, and n for theR³ group having Structure G5 are described herein and can be utilizedwithout limitation to describe the amine having Structure A7 which canbe utilized in the various aspects and/or embodiments described herein.

In an aspect, the amine having Structure A1 or Structure A5 can beaniline, a substituted aniline, a naphthylamine, or a substitutednaphthylamine. In an embodiment, R¹ can be aniline or a substitutedaniline; alternatively, a naphthylamine or a substituted naphthylamine;alternatively, an aniline or a naphthylamine; or alternatively, asubstituted aniline or a substituted naphthylamine. Substituents andsubstituents patterns for R¹ and R³ are described herein and can beutilized without limitation to further describe the substituted anilinesand substituted naphthylamines which can be utilized in aspects and/orembodiments described herein.

In an embodiment, the amine having Structure A1 or Structure A5 can be a2-substituted aniline, a 3-substituted aniline, a 4-substituted aniline,a 2,4-disubstituted aniline, a 2,6-disubstituted aniline,3,5-disubstituted aniline, or a 2,4,6-trisubstituted aniline. In otherembodiments, the R¹ substituted aniline can be a 2-substituted aniline,a 4-substituted aniline, a 2,4-disubstituted aniline, or a2,6-disubstituted aniline; alternatively, a 3-substituted aniline or a3,5-disubstituted aniline; alternatively, a 2-substituted aniline or a4-substituted aniline; alternatively, a 2,4-disubstituted aniline or a2,6-disubstituted aniline; alternatively, a 2-substituted aniline;alternatively, a 3-substituted aniline; alternatively, a 4-substitutedaniline; alternatively, a 2,4-disubstituted aniline; alternatively, a2,6-disubstituted aniline; alternatively, 3,5-disubstituted aniline; oralternatively, a 2,4,6-trisubstituted aniline. Substituents for the R¹and R³ phenyl groups are generally disclosed herein and can be utilizedwithout limitation to further describe the substituted anilines whichcan be utilized in the various aspects and/or embodiments describedherein.

In an embodiment, the amine having Structure A1 or Structure A5 can be1-naphthylamine, a substituted 1-naphthylamine, 2-naphthylamine, or asubstituted 2-naphthylamine. In some embodiments, the amine havingStructure A1 or Structure A5 can be 1-naphthylamine or a substituted1-naphthylamine; alternatively, 2-naphthylamine or a substituted2-naphthylamine; alternatively, 1-naphthylamine; alternatively, asubstituted 1-naphthylamine; alternatively, 2-naphthylamine; oralternatively, a substituted 2-naphthylamine. In other embodiments, theamine having Structure A1 or Structure A4 can be a 2-substituted1-naphthylamine, a 3-substituted 1-naphthylamine, a 4-substituted1-naphthylamine, or a 8-substituted 1-naphthylamine; alternatively, a2-substituted 1-naphthylamine; alternatively, a 3-substituted1-naphthylamine; alternatively, a 4-substituted 1-naphthylamine; oralternatively, a 8-substituted 1-naphthylamine. In further embodiments,the amine having Structure A1 or Structure A5 can be a 1-substituted2-naphthylamine, a 3-substituted 2-naphthylamine, or a 4-substituted2-naphthylamine, or a 1,3-disubstituted 2-naphthylamine; alternatively,a 1-substituted 2-naphthylamine; alternatively, a 3-substituted2-naphthylamine; alternatively, a 4-substituted 2-naphthylamine;alternatively, or a 1,3-disubstituted 2-naphthylamine. Substituents forthe R¹ and R³ naphthyl groups are generally disclosed herein and can beutilized without limitation to further describe the substitutednaphthylamines which can be utilized in the various aspects and/orembodiments described herein.

In an aspect, the amine having Structure A1 can have Structure A8. In anaspect, the amine having Structure A5 can have Structure A9.

The R¹², R¹³, R¹⁴, R¹⁵, and R¹⁶ substituents and substituent patternsfor the R¹ group having Structure G2 are described herein and can beutilized without limitation to describe the amine having Structure A8which can be utilized in the various aspects and embodiments describedherein. The R³², R³³, R³⁴, R³⁵, and R³⁶ substituents and substituentpatterns for the R³ group having Structure G6 are described herein andcan be utilized without limitation to describe the amine havingStructure A9 which can be utilized in the various aspects and/orembodiments described herein.

In an aspect, the amine having Structure A1 or Structure A5 can be anaminopyridine, a substituted aminopyridine, an aminofuran, a substitutedaminofuran, an aminothiophene, or a substituted aminothiophene. In anembodiment, the amine having Structure A1 or Structure A5 can be anamino-pyridine or a substituted aminopyridine; alternatively, anaminofuran or a substituted aminofuran; or alternatively, anaminothiophene, or a substituted aminothiophene. In some embodiments,the amine having Structure A1 or Structure A5 can be an aminopyridine,an aminofuran, or an aminothiophene. In other embodiments, the aminehaving Structure A1 or Structure A5 can be an aminopyridine;alternatively, a substituted aminopyridine; alternatively, anaminofuran; alternatively, a substituted aminofuran; alternatively, anaminothiophene; or alternatively, a substituted aminothiophene.

In an embodiment, the amine having Structure A1 or Structure A5 can be2-aminopyridine, a substituted 2-aminopyridine, 3-aminopyridine, asubstituted 3-aminopyridine, 4-aminopyridine, or a substituted4-aminopyridine; alternatively, 2-aminopyridine, 3-aminopyridine, or4-aminopyridine. In some embodiments, the amine having Structure A1 orStructure A5 can be 2-aminopyridine or a substituted 2-aminopyridine;alternatively, 3-aminopyridine or a substituted pyridin-3-yl group;alternatively, 4-aminopyridine or a substituted pyridin-4-yl group;alternatively, 2-aminopyridine; alternatively, a substituted2-aminopyridine; alternatively, 3-aminopyridine; alternatively, asubstituted pyridin-3-yl group; alternatively, 4-aminopyridine; oralternatively, a substituted pyridin-4-yl group. In an embodiment, theamine having Structure A1 or Structure A5 can be a 2-substituted3-aminopyridine, a 4-substituted 3-aminopyridine, a 5-substituted3-aminopyridine, a 6-substituted 3-aminopyridine, a 2,4-disubstituted3-aminopyridine, a 2,6-disubstituted 3-aminopyridine, or a2,4,6-trisubstituted 3-amino-pyridine; alternatively, 2-substituted3-aminopyridine, a 4-substituted 3-aminopyridine, a 6-substituted3-aminopyridine; alternatively, a 2,4-disubstituted 3-aminopyridine or a2,6-disubstituted 3-aminopyridine; alternatively, a 2-substituted3-aminopyridine; alternatively, a 4-substituted 3-aminopyridine;alternatively, a 5-substituted 3-aminopyridine; alternatively, a6-substituted 3-aminopyridine; alternatively, a 2,4-disubstituted3-aminopyridine; alternatively, a 2,6-disubstituted 3-aminopyridine; oralternatively, a 2,4,6-trisubstituted 3-aminopyridine. In an embodiment,the amine having Structure A1 or Structure A5 can be a 2-substituted4-aminopyridine, a 3-substituted 4-aminopyridine, a 5-substituted4-aminopyridine, a 6-substituted 4-aminopyridine, a 2,6-disubstituted4-aminopyridine, or a 3,5-disubstituted 4-aminopyridine; alternatively,2-substituted 4-aminopyridine, a 6-substituted 4-amino-pyridine;alternatively, a 3-substituted 4-aminopyridine or a 5-substituted4-aminopyridine; alternatively, a 2-substituted 4-aminopyridine;alternatively, a 3-substituted 4-aminopyridine; alternatively, a5-substituted 4-aminopyridine; alternatively, a 6-substituted4-aminopyridine; alternatively, a 2,6-disubstituted 4-aminopyridine; oralternatively, a 3,5-disubstituted 4-aminopyridine. Substituents for theR¹ and R³ pyridinyl groups are generally disclosed herein and can beutilized without limitation to further describe the substitutedaminopyridines which can be utilized in the various aspects and/orembodiments described herein.

In an embodiment, the amine having Structure A1 or Structure A5 can be2-aminofuran, a substituted 2-aminofuran, 3-aminofuran, or a substituted3-aminofuran; alternatively, fur-2-yl or 3-amino-furan. In someembodiments, the amine having Structure A1 or Structure A5 can be2-aminofuran or a substituted 2-aminofuran; alternatively, 3-aminofuran,or a substituted 3-aminofuran; alternatively, 2-aminofuran;alternatively, a substituted 2-aminofuran; alternatively, 3-aminofuran;or alternatively, a substituted 3-aminofuran. In an embodiment, theamine having Structure A1 or Structure A5 can be a 2-substituted3-aminofuran, a 4-substituted 3-aminofuran, or a 2,4-disubstituted3-aminofuran; alternatively, a 2-substituted 3-aminofuran;alternatively, a 4-substituted 3-aminofuran; or alternatively, a2,4-disubstituted 3-aminofuran. Substituents for the R¹ and R³ furangroups are generally disclosed herein and can be utilized withoutlimitation to further describe the substituted aminofurans which can beutilized in the various aspects and/or embodiments described herein.

In an embodiment, the amine having Structure A1 or Structure A5 can be2-aminothiophene, a substituted 2-aminothiophene, 3-aminothiophene, or asubstituted 3-aminothiophene; alternatively, 2-aminothiophene or3-aminothiophene. In some embodiments, the amine having Structure A1 orStructure A5 can be 2-aminothiophene or a substituted thien-2-yl group;alternatively, 3-aminothiophene or a substituted thien-3-yl group;alternatively, 2-aminothiophene; alternatively, a substituted thien-2-ylgroup; alternatively, 3-aminothiophene; or alternatively, a substituted3-aminothiophene. In an embodiment, the amine having Structure A1 orStructure A5 can be a 2-substituted 3-aminothiophene, a 4-substituted3-aminothiophene, or a 2,4-disubstituted 3-aminothiophene;alternatively, a 2-substituted 3-amino-thiophene; alternatively, a4-substituted 3-aminothiophene; or alternatively, a 2,4-disubstituted3-aminothiophene. Substituents for the R¹ and R³ thienyl groups aregenerally disclosed herein and can be utilized without limitation tofurther describe the substituted aminothiophenes which can be utilizedin the various aspects and/or embodiments described herein.

In a non-limiting embodiment, the amine having Structure A1 or StructureA5 can be aniline, a 2-alkylaniline, a 3-alkylaniline, a 4-alkylaniline,a 2,4-dialkylaniline a 2,6-dialkylaniline, a 3,5-dialkyl-aniline, or a2,4,6-trialkylaniline; alternatively, a 2-alkylaniline, a4-alkylaniline, a 2,4-dialkylaniline, a 2,6-dialkylaniline, or a2,4,6-trialkylaniline; alternatively, a 2-alkylaniline or a4-alkylaniline; alternatively, a 2,4-dialkylaniline a2,6-dialkylaniline; alternatively, a 3-alkylaniline or a3,5-dialkyl-aniline; alternatively, a 2-alkylaniline or a2,6-dialkylaniline; alternatively, a 2-alkylaniline; alternatively, a3-alkylaniline; alternatively, a 4-alkylaniline; alternatively, a2,4-dialkylaniline; alternatively, a 2,6-dialkylaniline; alternatively,a 3,5-dialkylaniline; or alternatively, a 2,4,6-trialkylaniline. Inanother non-limiting embodiment, the amine having Structure A1 orStructure A5 can be a 1-aminonaphthylene, a 2-aminonaphthylene, a2-alkylnaphth-1-yl group, a 1-alkyl-2-aminonaphthylene, a3-alkylnapth-2-yl group, or a 1,3-dialkyl-2-aminonaphthylene;alternatively, a 1-aminonaphthylene or a 2-alkyl-1-amino-naphthylene;alternatively, a 2-aminonaphthylene, a 1-alkyl-2-aminonaphthylene, a3-alkylamin-napthylene, or a 1,3-dialkyl-2-aminonaphthylene;alternatively, 1-aminonaphthylene; alternatively, a 2-aminonaphthylene;alternatively, a 2-alkyl-1-aminonaphthylene; alternatively, a1-alkyl-2-amino-naphthylene; alternatively, a 3-alkyl-2-aminonapthylene;or alternatively, a 1,3-dialkyl-2-amino-naphthylene. In othernon-limiting embodiments, the amine having Structure A1 or Structure A5can be a cyclohexylamine, a 2-alkylcyclohexylamine, or a2,6-dialkylcyclohexylamine; alternatively, cyclopentyl-amine, a2-alkylcyclopentylamine, or a 2,5-dialkylcyclopentylamine;alternatively, cyclohexylamine; alternatively, a 2-alkylcyclohexylamine;alternatively, a 2,6-dialkylcyclohexylamine; alternatively,cyclopentylamine; alternatively, a 2-alkylcyclopentylamine; oralternatively, 2,5-dialkylcyclopentyl-amine. Alkyl group substituentsare independently described herein and can be utilized, withoutlimitation, to further describe the alkylanilines, dialkylanilines,trialkylanilines, alkylaminonaphthylenes, dialkylaminonaphthylenes,alkylcyclohexylamines, dialkylcyclohexylamines, alkylcyclopentylamines,or dialkylcyclopentylamine which can be utilized in the various aspectsand/or embodiments described herein. Generally, the alkyl substitutentsof a dialkyl or trialkyl anilines, aminonaphthylenes, cyclohexylamines,or cyclopentylamines can be the same; or alternatively, can bedifferent.

In another non-limiting embodiment, the amine having Structure A1 orStructure A5 can be aniline, a 2-alkoxyaniline, a 3-alkoxyaniline, a4-alkoxyaniline, or a 3,5-dialkoxyaniline; alternatively, a2-alkoxyaniline or a 4-alkoxyaniline; alternatively, a 3-alkoxyanilineor 3,5-dialkoxyaniline; alternatively, a 2-alkoxyaniline; alternatively,a 3-alkoxyaniline; alternatively, a 4-alkoxyaniline; alternatively, a3,5-dialkoxyaniline. Alkoxy group substituents are independentlydescribed herein and can be utilized, without limitation, to furtherdescribe the alkoxyanilines or dialkoxyanilines which can be utilized inthe various aspects and/or embodiments described herein. Generally, thealkoxy substitutents of a dialkoxyaniline can be the same; oralternatively, can be different.

In other non-limiting embodiments, the amine having Structure A1 orStructure A5 can be aniline, a 2-haloaniline, a 3-haloaniline, a4-haloaniline, a 2,6-dihalophenyl group, or a 3,5-dialkylaniline;alternatively, a 2-haloaniline, a 4-haloaniline, or a 2,6-dihaloaniline;alternatively, a 2-haloaniline or a 4-haloaniline; alternatively, a3-haloaniline or a 3,5-dihaloaniline; alternatively, a 2-haloaniline;alternatively, a 3-haloaniline; alternatively, a 4-haloaniline;alternatively, a 2,6-dihaloaniline; or alternatively, a3,5-dialkylaniline. Halides are independently described herein and canbe utilized, without limitation, to further describe the haloanilines ordihaloanilines which can be utilized in the various aspects and/orembodiments described herein. Generally, the halides of a dihaloanilinecan be the same; or alternatively, can be different.

In a non-limiting embodiment, the amine having Structure A1 or StructureA5 can be 2-methylaniline, 2-ethylaniline, 2-n-propylaniline,2-isopropylaniline, 2-tert-butylaniline, 3-methylaniline,2,6-dimethylaniline, 2,6-diethylaniline, 2,6-di-n-propylaniline,2,6-diisopropylaniline, 2,6-di-tert-butylaniline,2-isopropyl-6-methylaniline, or 2,4,6-trimethylaniline; alternatively,2-methylaniline, 2-ethylaniline, 2-n-propylaniline, 2-isopropylaniline,or 2-tert-butylaniline; alternatively, 2,6-dimethyl-aniline,2,6-diethylaniline, 2,6-di-n-propylaniline, 2,6-diisopropylaniline,2,6-di-tert-butylaniline, or 2-isopropyl-6-methylaniline; alternatively,2-methylaniline; alternatively, 2-ethylaniline; alternatively,2-n-propylaniline; alternatively, 2-isopropylaniline; alternatively,2-tert-butylaniline; alternatively, 3-methyl-aniline; alternatively,2,6-dimethylaniline; alternatively, 2,6-diethylaniline; alternatively,2,6-di-n-propylaniline; alternatively, 2,6-diisopropylaniline;alternatively, 2,6-di-tert-butylaniline; alternatively,2-isopropyl-6-methylaniline; alternatively, 3,5-dimethylaniline; oralternatively, 2,4,6-trimethylaniline. In another non-limitingembodiment, the amine having Structure A1 or Structure A5 can be2-methyl-cyclohexylamine, 2-ethylcyclohexylamine,2-isopropylcyclohexylamine, 2-tert-butylcyclohexylamine,2,6-dimethylcyclohexylamine, 2,6-diethylcyclohexylamine,2,6-diisopropylcyclohexylamine, or 2,6-di-tert-butylcyclohexylamine;alternatively, 2-methylcyclohexylamine, 2-ethylcyclohexylamine,2-isopropylcyclohexylamine, or 2-tert-butylcyclohexylamine;alternatively, 2,6-dimethylcyclohexylamine, 2,6-diethylcyclohexylamine,2,6-diisopropylcyclohexylamine, or 2,6-di-tert-butylcyclohexylamine;alternatively, 2-methylcyclohexylamine; alternatively,2-ethylcyclohexylamine; alternatively, 2-isopropylcyclohexylamine;alternatively, 2-tert-butylcyclohexylamine; alternatively,2,6-dimethyl-cyclohexylamine; alternatively, 2,6-diethylcyclohexylamine;alternatively, 2,6-diisopropylcyclohexyl-amine; or alternatively, or2,6-di-tert-butylcyclohexylamine. In another non-limiting embodiment,the amine having Structure A1 or Structure A5 can be2-methyl-1-aminonaphthylene, 2-ethyl-1-amino-naphthylene group,2-n-propyl-1-aminonaphthylene, 2-isopropyl-1-aminoenaphthylene group, or2-tert-butyl-1-aminonaphthylene group; alternatively,2-methyl-1-aminonaphthylene group; alternatively,2-ethyl-1-aminonaphthylene group; alternatively,2-n-propyl-1-aminonaphthylene group; alternatively,2-isopropyl-1-naphthylene group; or alternatively,2-tert-butyl-1-amononaphthylene group.

In a non-limiting embodiment, the amine having Structure A1 or StructureA5 can be a 3-methoxyaniline, 3-ethoxyaniline, 3-isoprooxyaniline,3-tert-butoxyaniline, 4-methoxyaniline, 4-ethoxyaniline,4-isopropoxyaniline, 4-tert-butoxyaniline, 3,5-dimethoxyaniline,3,5-diethoxyaniline, 3,5-diisopropoxyaniline, or3,5-di-tert-butoxyaniline; alternatively, 3-methoxyaniline,3-ethoxyaniline, 3-isopropoxyaniline, or 3-tert-butoxyaniline;alternatively, 4-methoxyaniline, 4-ethoxyaniline, 4-isopropoxyaniline,or 4-tert-butoxyaniline; or alternatively, 3,5-dimethoxyaniline,3,5-diethoxyaniline, 3,5-diisopropoxyaniline, or3,5-di-tert-butoxyaniline. In other non-limiting embodiments, the aminehaving Structure A1 or Structure A5 can be 3-methoxyaniline;alternatively, 3-ethoxyaniline; alternatively, 3-isopropoxyaniline;alternatively, 3-tert-butoxyaniline; alternatively, 4-methoxyaniline;alternatively, 4-ethoxyaniline; alternatively, 4-isopropoxyaniline;alternatively, 4-tert-butoxyaniline; alternatively,3,5-dimethoxyaniline; alternatively, 3,5-diethoxyaniline; alternatively,3,5-diisopropoxyaniline; or alternatively, 3,5-di-tert-butoxyaniline.

In an aspect, the amine having Structure A1 can be a hydrocarbylhydrazine or an N,N-dihydrocarbyl hydrazine; alternatively, ahydrocarbyl hydrazine; or alternatively, an N,N-dihydrocarbyl hydrazine.Hydrocarbyl groups for R¹, hydrocarbylaminyl groups anddihydrocarbylaminyl groups have been described herein and these can beutilized, without limitation to further describe the N-hydrocarbylhydrazines and N,N-dihydrocarbyl hydrazines which can be utilized as theamine having Structure A1 in the various aspects and/or embodimentsdescribed herein. In some non-limiting embodiments, the amine havingStructure A1 can be methyl hydrazine, ethyl hydrazine, ispropylhydrazine, tert-butyl hydrazine, neopentyl hydrazine, N,N-dimethylhydrazine, N,N-diethyl hydrazine, N,N-diispropyl hydrazine,N,N-ditert-butyl hydrazine, or N,N-dineopentyl hydrazine; alternatively,methyl hydrazine, ethyl hydrazine, ispropyl hydrazine, tert-butylhydrazine, or neopentyl hydrazine; alternatively, N,N-dimethylhydrazine, N,N-diethyl hydrazine, N,N-diispropyl hydrazine,N,N-ditert-butyl hydrazine, or N,N-dineopentyl hydrazine; alternatively,methyl hydrazine; alternatively, ethyl hydrazine; alternatively,isopropyl hydrazine; alternatively, tert-butyl hydrazine; alternatively,neopentyl hydrazine; alternatively, dimethyl hydrazine; alternatively,N,N-diethyl hydrazine; alternatively, N,N-diisopropyl hydrazine;alternatively, N,N-ditert-butyl hydrazine; or alternatively,N,N-dineopentyl hydrazine. In other non-limiting embodiments, the aminehaving Structure A1 can be cyclopentylhydrazine, cyclohexylhydrazine,N,N-dicyclopentylhydrazine, N,N-dicyclohexylhydrazine; alternatively,cyclopentylhydrazine or cyclohexylhydrazine; alternatively,N,N-dicyclopentylhydrazine or N,N-dicyclohexylhydrazine; alternatively,cyclopentylhydrazine; alternatively, cyclohexylhydrazine; alternatively,N,N-dicyclopentylhydrazine; or alternatively, N,N-dicyclohexylhydrazine.In other non-limiting embodiments, the amine having Structure A1 can bephenylhydrazine, a substituted phenyl phenylhydrazine,N,N-diphenylhydrazine, or a substituted phenyl N,N-diphenylhydrazine;alternatively, phenylhydrazine, or a substituted phenyl phenylhydrazine;alternatively, N,N-diphenylhydrazine or a substituted phenylN,N-diphenylhydrazine; alternatively, phenylhydrazine orN,N-diphenylhydrazine; alternatively, phenylhydrazine; alternatively, asubstituted phenyl phenylhydrazine; alternatively,N,N-diphenylhydrazine; or alternatively, a substituted phenylN,N-diphenylhydrazine. Substituents and substituent patterns forsubstituted phenylaminyl groups and diphenylaminyl groups are generallydisclosed herein and can be utilized without limitation to furtherdescribe the substituted phenyl phenylhydrazines and substituted phenylN,N-diphenylhydrazines which can be utilized as the amine havingStructure A1 in the various aspects and/or embodiments described herein.

In an aspect, the amine having Structure A1 can be a 1-aminylcycloamineor a cycloamine substituted 1-aminylcycloamine; alternatively, a1-aminylcycloamine; or alternatively, a cycloamine substituted1-aminylcycloamine. Cycloaminyl groups and substituted cycloaminylgroups have been described herein and these can be utilized, withoutlimitation to further describe the N,N-dihydrocarbyl hydrazine which canbe utilized as the amine having Structures A2 in the various aspectsand/or embodiments described herein. In some non-limiting embodiments,the amine having Structure A1 can be 1-aminopyrrolidine, a substitutedpyrrolidine 1-aminopyrrolidine, 1-aminopiperidine, or a substitutedpiperidine 1-aminopiperidine; alternatively, 1-aminopyrrolidine or asubstituted pyrrolidine 1-aminopyrrolidine; alternatively,1-aminopiperidine or a substituted piperidine 1-aminopiperidine;alternatively, 1-aminopyrrolidine; alternatively, a substitutedpyrrolidine 1-aminopyrrolidine; alternatively, 1-aminopiperidine; oralternatively, a substituted piperidine 1-aminopiperidine. Substituentsand substituent patterns for substituted cycloaminyl groups aregenerally disclosed herein and can be utilized without limitation tofurther describe the cycloaminyl substituted 1-aminocycloamines whichcan be utilized as the amine having Structure A1 in the various aspectsand/or embodiments described herein.

In an aspect, L¹ of the amine having Structure A2 can be any L¹described herein. L¹ is described herein as a feature of theN²-phosphinyl amidine metal salt complexes utilized in various aspectsof this disclosure. Since the amines having structure A2 can be utilizedto prepare embodiments of the N²-phospinyl amidine compounds havingStructure NP2 or Structure NP7, the aspect and embodiments of L¹ canutilized without limitation to further describe the amines havingStructures A2.

In an aspect, the amine having Structure A2 can be a diaminomethane, adiaminoethane, a diaminopropane, a diaminobutane, a diaminopentane, adiaminohexane, a diaminoheptane, a diamino-octane, a diaminononane, adiaminodecane, a diaminoundecane, a diaminododecane, a diaminotridecane,a diaminotetradecane, a diaminopentadecane, a diaminohexadecane, adiaminoheptadecane, a diamino-octadecane, or a diaminononadecane; oralternatively, a diaminomethane, a diaminoethane, a diamino-propane, adiaminobutane, a diaminopentane, a diaminohexane, a diaminoheptane, adiaminooctane, a diaminononane, or a diaminodecane. In some embodiments,the amine having Structure A2 can be a diaminomethane, a diaminoethane,a diaminopropane, a diaminobutane, or a diaminopentane. In otherembodiments, the amine having Structure A2 can be a diaminomethane;alternatively, a diaminoethane; alternatively, a diaminopropane;alternatively, a diaminobutane; alternatively, a diaminopentane;alternatively, a diaminohexane; alternatively, a diaminoheptane;alternatively, a diaminooctane; alternatively, a diaminononane;alternatively, a diaminodecane; alternatively, a diaminoundecane;alternatively, a diaminododecane; alternatively, a diaminotridecane;alternatively, a diaminotetradecane; alternatively, adiaminopentadecane; alternatively, a diaminohexadecane; alternatively, adiamino-heptadecane; alternatively, a diaminooctadecane; oralternatively, a diaminononadecane. In some embodiments, the aminehaving Structure A2 can be 1,2-diaminoethane, 1,3-diaminopropane,1,4-diaminobutane, 2,3-diaminobutane, 1,5-diaminopentane,1,3-diamino-2,2-dimethylpropane, 1,6-diaminohexane, or2,3-diamino-2,3-dimethylbutane; alternatively, 1,2-diaminoethane,1,3-diamino-propane, 1,4-diaminobutane, 1,5-diaminopentane, or1,6-diaminohexane; alternatively, 1,2-diaminoethane; alternatively,1,3-diaminopropane; alternatively, 1,4-diaminobutane; alternatively,2,3-diaminobutane; alternatively, 1,5-diaminopentane; alternatively,1,3-diamino-2,2-dimethylpropane; alternatively, 1,6-diaminohexane; oralternatively, 2,3-diamino-2,3-dimethylbutane.

In an aspect, the amine having Structure A2 can have the formulaH₂N—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—C≡NH₂. R^(1a), R^(2a), R^(3a),R^(4a), and t are described herein as embodiments of an L¹ group havingstructure —CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—. The descriptions ofR^(1a), R^(2a), R^(3a), R^(4a), and t can be utilized without limitationto further describe the amines having the formulaH₂N—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—NH₂ which can be utilized in thevarious aspects and/or embodiments described herein.

In an embodiment, the amine having Structure A2 can be adiaminocyclobutane, a substituted diaminocyclobutane, adiaminocyclopentane, a substituted diaminocyclopentane, adiaminocyclohexane, a substituted diaminocyclohexane, adiaminocycloheptane, a substituted diaminocycloheptane, adiaminocyclooctane, or a substituted diaminocyclooctane. In someembodiments, the amine having Structure A2 can be a diaminocyclopentane,a substituted diaminocyclopentane, a diaminocyclohexane, a substituteddiaminocyclohexane. In other embodiments, the amine having Structure A2can be a diaminocyclobutane or a substituted diaminocyclobutane;alternatively, a diaminocyclopentane or a substituteddiaminocyclopentane; alternatively, a diaminocyclohexane or asubstituted diamino-cyclohexane; alternatively, a diaminocycloheptane ora substituted diaminocycloheptane; or alternatively, adiaminocyclooctane, or a substituted diaminocyclooctane. In furtherembodiments, the amine having Structure A2 can be a diaminocyclopentane;alternatively, a substituted diaminocyclopentane; a diaminocyclohexane;or alternatively, a substituted diaminocyclohexane.

In an embodiment, the amine having Structure A2 can be1,3-diaminocyclopentane, a substituted 1,3-diaminocyclopentane,1,3-diaminocyclohexane, a substituted 1,3-diaminocyclohexane,1,4-diaminocyclohexane, or a substituted 1,4-diaminocyclohexane;alternatively, 1,3-diamino-cyclopentane, 1,3-diaminocyclohexane, or1,4-diaminocyclohexane. In some embodiments, the amine having StructureA2 can be 1,3-diaminocyclopentane or a substituted1,3-diaminocyclopentane; alternatively, 1,3-diaminocyclohexane, asubstituted 1,3-diaminocyclohexane, 1,3-diaminocyclohexane, or asubstituted 1,4-diaminocyclohexane; alternatively,1,3-diaminocyclohexane or a substituted 1,3-diaminocyclohexane;alternatively, 1,4-diaminocyclohexane or a substituted1,4-diaminocyclohexane; alternatively, 1,3-cyclopentane; alternatively,1,3-diaminocyclohexane; or alternatively, 1,4-diaminocyclohexane.

In a non-limiting embodiment, the amine having Structure A2 can be a2-disubstituted 1,3-diaminocyclopenane group, a 4,5-disubstituted1,3-diaminocyclopenane group, a 2,5-disubstituted 1,3-diaminocyclopenanegroup, or a 2,4,5-trisubstituted 1,3-diaminocyclopenane group. In someembodiments, the amine having Structure A2 can be a 2-disubstituted1,3-diaminocyclopenane group; alternatively, a 4,5-disubstituted1,3-diaminocyclopenane group; alternatively, a 2,5-disubstituted1,3-diaminocyclopenane group; alternatively, or a 2,4,5-trisubstituted1,3-diaminocyclopenane group. In another non-limiting embodiment, theamine having Structure A2 can be a 2,6-disubstituted1,4-diamino-cyclohexane group, a 2,3-disubstituted1,4-diaminocyclohexane group, a 2,5-disubstituted1,4-diamino-cyclohexane group, or a 2,3,5,6-tetrasubstituted1,4-diaminocyclohexane group. In some embodiments, the amine havingStructure A2 can be a 2,6-disubstituted 1,4-diaminocyclohexane group ora 2,5-disubstituted 1,4-diaminocyclohexane group; alternatively, a2,6-disubstituted 1,4-diaminocyclohexane group; alternatively, a2,3-disubstituted 1,4-diaminocyclohexane group; alternatively, a2,5-disubstituted 1,4-diaminocyclohexane group; or alternatively, a2,3,5,6-tetrasubstituted 1,4-diaminocyclohexane group.

L¹ substituents and substituent patterns for substituted L¹ cycloalkanegroups are generally disclosed herein and can be utilized withoutlimitation to further describe the substituted diamino-cycloalkaneswhich can be utilized as the amine having Structure A2 in the variousaspects and/or embodiments described herein.

In an aspect, the amine having Structure A2 can be a bi(aminocyclyl), asubstituted bi(amino-cyclyl), a bis(aminocyclyl)methane, a substitutedbis(aminocyclyl)methane, a bis(aminocyclyl)ethane, or a substitutedbis(aminocyclyl)ethane; or alternatively, a bis(aminocyclyl), abis(aminocyclyl)methane, or a bis(aminocyclyl)ethane. In an embodiment,the amine having Structure A2 can be a bi(aminocyclyl) or a substitutedbi(aminocyclyl); alternatively, a bis(aminocyclyl)methane or asubstituted bis(aminocyclyl)-methane; or alternatively, abis(aminocyclyl)ethane or a substituted bis(aminocyclyl)ethane. In someembodiments, the amine having Structure A2 can be a bi(aminocyclyl);alternatively, a substituted bi(aminocyclyl); alternatively, abis(aminocyclyl)methane; alternatively, a substitutedbis(aminocyclyl)-methane; alternatively, a bis(aminocyclyl)ethane; oralternatively, a substituted bis(aminocyclyl)ethane. In an aspect, theamine having Structure A2 can be a bi(aminocyclohexyl), a substitutedbi(amino-cyclohexyl), a bis(aminocyclohexyl)methane, a substitutedbis(aminocyclohexyl)methane, a bis(amino-cyclohexyl)ethane, or asubstituted bis(aminocyclohexyl)ethane; or alternatively, abi(aminocyclohexyl), a bis(aminocyclohexyl)methane, or abis(aminocyclohexyl)ethane. In an embodiment, the amine having StructureA2 can be a bi(aminocyclohexyl) or a substituted bi(aminocyclohexyl);alternatively, a bis(aminocyclohexyl)methane or a substitutedbis(aminocyclohexyl)methane; or alternatively, abis(aminocyclohexyl)ethane or a substituted bis(aminocyclohexyl)ethane.In some embodiments, the amine having Structure A2 can be abi(aminocyclohexyl); alternatively, a substituted bi(amino-cyclohexyl);alternatively, a bis(aminocyclohexyl)methane; alternatively, asubstituted bis(amino-cyclohexyl)methane; alternatively, abis(aminocyclohexyl)ethane; or alternatively, a substitutedbis(aminocyclohexyl)ethane. L¹ substituents and substituent patterns forsubstituted L¹ bicyclylene groups, bis(cyclylene)methane groups, andbis(cyclylene)ethane groups are generally disclosed herein and can beutilized without limitation to further describe the substitutedbi(aminocyclyl)s, substituted bis(aminocyclyl)methanes, and substitutedbis(aminocyclyl)ethanes which can be utilized as the amine havingstructure A2 in the various aspects and/or embodiments described herein.

In an embodiment, the amine having Structure A2 can be a4,4′-bicyclohexyldiamine, a 3,3′-disubstituted-4,4′-bicyclohexyldiamine,a 3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldiamine,bis(4-aminocyclohexyl)methane, abis(3-substituted-4-aminocyclohexyl)methane, abis(3,5-disubstituted-4-aminocyclohexyl)methane,bis-1,2-(4-aminocyclohexyl)ethane, abis-1,2-(3-substituted-4-amino-cyclohexyl)ethane, or abis-1,2-(3,5-disubstituted-4-aminocyclohexyl)ethane. In someembodiments, the amine having Structure A2 can be a4,4′-bicyclohexyldiamine, a3,3′-disubstituted-4,4′-bicyclohexyl-diamine, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldiamine; alternatively, abis(4-aminocyclohexyl)-methane, abis(3-substituted-4-aminocyclohexyl)methane or abis(3,5-disubstituted-4-aminocyclohexyl)-methane; alternatively, abis-1,2-(4-aminocyclohexyl)ethane, abis-1,2-(3-substituted-4-amino-cyclohexyl)ethane or abis-1,2-(3,5-disubstituted-4-aminocyclohexyl)ethane. In otherembodiments, the amine having Structure A2 can be a4,4′-bicyclohexyldiamine; alternatively, a3,3′-disubstituted-4,4′-bicyclohexyldiamine; alternatively, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldiamine; alternatively, abis(4-aminocyclohexyl)methane; alternatively, abis(3-substituted-4-aminocyclohexyl)methane; alternatively, abis(3,5-disubstituted-4-aminocyclohexyl)methane; alternatively, abis-1,2-(4-amino-cyclohexyl)ethane; alternatively, abis-1,2-(3-substituted-4-aminocyclohexyl)ethane; or alternatively, abis-1,2-(3,5-disubstituted-4-aminocyclohexyl)ethane. Generally, anybis(aminocyclohexyl)ethane disclosed herein (substituted orunsubstituted) can be a bis-1,1-(aminocyclohexyl)ethane or abis-1,2-(aminocyclohexyl)ethane group; alternatively, abis-1,1-(aminocyclohexyl)ethane; or alternatively, abis-1,2-(aminocyclohexyl)ethane. Substituents for the substituted L¹bicyclohex-4,4′-ylene groups, bis(cyclohex-4-ylene)methane groups, and abis-1,2-(cyclohex-4-ylene)ethane groups are generally disclosed hereinand can be utilized without limitation to further describe thesubstituted 4,4′-bicyclohexyldiamines, substitutedbis(4-aminocyclohexyl)methanes, and substitutedbis-1,2-(4-amino-cyclohexyl)ethanes which can be utilized as the aminehaving structure A2 in the various aspects and/or embodiments describedherein.

In an aspect, the amine having Structure A2 can be a diaminobenzene or asubstituted diaminobenzene. In an embodiment, the amine having StructureA2 can be a diaminobenzene; or alternatively, a substituteddiaminobenzene. In some embodiments, the amine having Structure A2 canbe 1,2-diaminobenzene or a substituted 1,2-diaminobenzene;alternatively, a 1,2-diaminobenzene; or alternatively, a substituted1,2-diaminobenzene. In other embodiments, the amine having Structure A2can be a 1,3-diaminobenzene or a substituted 1,3-diaminobenzene;alternatively, a 1,3-diaminobenzene; or alternatively, a substituted1,3-diaminobenzene. In yet other embodiments, the amine having StructureA2 can be a 1,4-diaminobenzene or a substituted 1,4-diaminobenzene;alternatively, a 1,4-diamino-benzene; or alternatively, a substituted1,4-diaminobenzene. In further embodiments, the amine having StructureA2 can be a 1,2-diaminobenzene, a 1,3-diaminobenzene, or a1,4-diaminobenzene; alternatively, a 1,3-diaminobenzene, or a1,4-diaminobenzene. In other embodiments, the amine having Structure A2can be a substituted 1,2-diaminobenzene, a substituted1,3-diaminobenzene, or a substituted 1,4-diaminobenzene; alternatively,a substituted 1,3-diaminobenzene, or a substituted 1,4-diamino-benzene.In a non-limiting embodiment, the amine having Structure A2 can be a2,6-disubstituted 1,4-diaminobenzene, a 2,3-disubstituted1,4-diaminobenzene, a 2,5-disubstituted 1,4-diaminobenzene, or a2,3,5,6-tetrasubstituted 1,4-diaminobenzene. In some embodiments, theamine having Structure A2 can be a 2,6-disubstituted 1,4-diaminobenzeneor a 2,5-disubstituted 1,4-diaminobenzene; alternatively, a2,6-disubstituted 1,4-diaminobenzene; alternatively, a 2,3-disubstituted1,4-diaminobenzene; alternatively, a 2,5-disubstituted1,4-diaminobenzene; or alternatively, a 2,3,5,6-tetrasubstituted1,4-diaminobenzene. L′ substituents and substituent patterns forsubstituted L¹ phenylene groups are generally disclosed herein and canbe utilized without limitation to further describe the substituteddiaminobenzenes which can be utilized as the amine having structure A2in the various aspects and/or embodiments described herein.

In an aspect, the amine having Structure A2 can be a diaminonaphthaleneor a substituted diaminonaphthalene. In an embodiment, the amine havingStructure A2 can be a diaminonaphthalene; or alternatively, asubstituted diaminonaphthalene. In some embodiments, the amine havingStructure A2 can be 1,3-diaminonaphthalene, a substituted1,3-diaminonaphthalene, 1,4-diaminonaphthalene, a substituted1,4-diaminonaphthalene, 1,5-diaminonaphthalene, a substituted1,5-diaminonaphthalene, 1,6-diaminonaphthalene, a substituted1,6-diaminonaphthalene, 1,7-diaminonaphthalene, a substituted1,7-diaminonaphthalene, 1,8-diaminonaphthalene, or a substituted1,8-diaminonaphthalene. In other embodiments, the amine having StructureA2 can be 1,3-diaminonaphthalene or a substituted1,3-diaminonaphthalene; alternatively, 1,4-diaminonaphthalene or asubstituted 1,4-diaminonaphthalene; alternatively,1,5-diaminonaphthalene or a substituted 1,5-diaminonaphthalene;alternatively, 1,6-diaminonaphthalene or a substituted1,6-diaminonaphthalene; alternatively, 1,7-diaminonaphthalene or asubstituted 1,7-diaminonaphthalene; or alternatively,1,8-diaminonaphthalene or a substituted 1,8-diaminonaphthalene. In yetother embodiments, the amine having Structure A2 can be1,3-diamino-naphthalene; alternatively, a substituted1,3-diaminonaphthalene; alternatively, 1,4-diaminonaphthalene;alternatively, a substituted 1,4-diaminonaphthalene; alternatively,1,5-diaminonaphthalene; alternatively, a substituted1,5-diaminonaphthalene; alternatively, 1,6-diaminonaphthalene;alternatively, a substituted 1,6-diaminonaphthalene; alternatively,1,7-diaminonaphthalene; alternatively, a substituted1,7-diamino-naphthalene; alternatively, 1,8-diaminonaphthalene; oralternatively, a substituted 1,8-diamino-naphthalene. L¹ substituentsand substituent patterns for substituted L¹ naphthylene groups aregenerally disclosed herein and can be utilized without limitation tofurther describe the substituted diamino-naphthalenes which can beutilized as the amine having structure A2 in the various aspects and/orembodiments described herein.

In an aspect, the amine having Structure A2 can be a bianiline, asubstituted bianiline, a bis(aminophenyl)methane group, a substitutedbis(aminophenyl)methane group, a bis(aminophenyl)-ethane group, or asubstituted bis(aminophenyl)ethane group; or alternatively, a bianiline,a bis(aminophenyl)methane group, or a bis(aminophenyl)ethane group. Inan embodiment, the amine having Structure A2 can be a bianiline or asubstituted bianiline; alternatively, a bis(aminophenyl)-methane groupor a substituted bis(aminophenyl)methane group; or alternatively, abis(aminophenyl)-ethane group or a substituted bis(aminophenyl)ethanegroup. In some embodiments, the amine having Structure A2 can be abianiline; alternatively, a substituted bianiline; alternatively, abis(aminophenyl)-methane group; alternatively, a substitutedbis(aminophenyl)methane group; alternatively, a bis(amino-phenyl)ethanegroup; or alternatively, a substituted bis(aminophenyl)ethane group.

In an embodiment, the amine having Structure A2 can be 2,2′-bianiline, asubstituted 2,2′-bianiline, 3,3′-bianiline, a substituted3,3′-bianiline, 4,4′-bianiline, or a substituted 4,4′-bianiline; oralternatively, 3,3′-bianiline, a substituted 3,3′-bianiline,4,4′-bianiline, or a substituted 4,4′-bianiline. In some embodiments,the amine having Structure A2 can be 2,2′-bianiline or a substituted2,2′-bianiline; alternatively, 3,3′-bianiline or a substituted3,3′-bianiline; or alternatively, 4,4′-bianiline or a substituted4,4′-bianiline. In other embodiments, the amine having Structure A2 canbe 2,2′-bianiline; alternatively, a substituted 2,2′-bianiline;alternatively, 3,3′-bianiline; alternatively, a substituted3,3′-bianiline; alternatively, 4,4′-bianiline; or alternatively, asubstituted 4,4′-bianiline.

In an embodiment, the amine having Structure A2 can bebis(2-aminophenyl)methane, a substituted bis(2-aminophenyl)methane,bis(3-aminophenyl)methane, a substituted bis(3-aminophenyl)-methane,bis(4-aminophenyl)methane, or a substituted bis(4-aminophenyl)methane;or alternatively, bis(3-aminophenyl)methane, a substitutedbis(3-aminophenyl)methane, bis(4-aminophenyl)methane, or a substitutedbis(4-aminophenyl)methane. In some embodiments, the amine havingStructure A2 can be bis(2-aminophenyl)methane or a substitutedbis(2-aminophenyl)methane; alternatively, bis(3-amino-phenyl)methane ora substituted bis(3-aminophenyl)methane; or alternatively,bis(4-aminophenyl)-methane or a substituted bis(4-aminophenyl)methane.In other embodiments, the amine having Structure A2 can bebis(2-aminophenyl)methane; alternatively, a substitutedbis(2-aminophenyl)methane; alternatively, bis(3-aminophenyl)methane;alternatively, a substituted bis(3-aminophenyl)methane; alternatively,bis(4-aminophenyl)methane; or alternatively, a substitutedbis(4-aminophenyl)methane.

In an embodiment, the amine having Structure A2 can bebis(2-aminophenyl)ethane, a substituted bis(2-aminophenyl)ethane,bis(3-aminophenyl)ethane, or a substituted bis(3-aminophenyl)-ethane,bis(4-aminophenyl)ethane, or a substituted bis(4-aminophenyl)ethane; oralternatively, bis(3-aminophenyl)ethane, a substitutedbis(3-aminophenyl)ethane, bis(4-aminophenyl)ethane, or a substitutedbis(4-aminophenyl)ethane. In some embodiments, the amine havingStructure A2 can be bis(2-amino-phenyl)ethane or a substitutedbis(2-aminophenyl)ethane; alternatively, bis(3-aminophenyl)ethane or asubstituted bis(3-aminophenyl)ethane; or alternatively,bis(4-aminophenyl)ethane or a substituted bis(4-aminophenyl)ethane. Inother embodiments, the amine having Structure A2 can bebis(2-aminophenyl)-ethane; alternatively, a substitutedbis(2-aminophenyl)ethane; alternatively, bis(3-aminophenyl)ethane;alternatively, a substituted bis(3-aminophenyl)ethane; alternatively,bis(4-aminophenyl)ethane; or alternatively, a substitutedbis(4-aminophenyl)ethane. Generally, any bis(aminophenyl)ethanedisclosed herein (substituted or unsubstituted) can be abis-1,1-(aminophenyl)ethane or a bis-1,2-(aminophenyl)ethane group;alternatively, a bis-1,1-(aminophenyl)ethane; or alternatively, abis-1,2-(aminophenyl)ethane.

In an embodiment, the amine having Structure A2 can be a3,3′-disubstituted-4,4′-bianiline, a3,3′,5,5′-tetrasubstituted-4,4′-bianiline, abis(3-substituted-4-aminophenyl)methane, abis(3,5-disubstituted-4-aminophenyl)methane, abis-1,2-(3-substituted-4-aminophenyl)ethane, abis-1,2-(3,5-disubstituted-4-aminophenyl)ethane. In some embodiments,the amine having Structure A2 can be a 3,3′-disubstituted 4,4′-bianilineor a 3,3′,5,5′-tetrasubstituted-4,4′-bianiline; alternatively, abis(3-substituted-4-aminophenyl)methane or abis(3,5-disubstituted-4-aminophenyl)methane; alternatively, abis-1,2-(3-substituted-4-aminophenyl)ethane or abis-1,2-(3,5-disubstituted-4-aminophenyl)ethane. In other embodiments,the amine having Structure A2 can be a3,3′-disubstituted-4,4′-bianiline; alternatively,3,3′,5,5′-tetrasubstituted-4,4′-bianiline; alternatively, abis(3-substituted-4-aminophenyl)methane; alternatively, abis(3,5-disubstituted-4-aminophenyl)methane; alternatively, abis-1,2-(3-substituted-4-aminophenyl)ethane; or alternatively, abis-1,2-(3,5-disubstituted-4-aminophenyl)ethane.

L¹ substituents and substituent patterns for general and specificsubstituted L¹ biphenylene groups, bis(phenylene)methane groups, andbis(phenylene)ethane groups are generally disclosed herein and can beutilized without limitation to further describe the general and specificsubstituted bianilines, substituted bis(aminophenyl)methanes, andsubstituted bis(aminophenyl)ethanes which can be utilized as the aminehaving structure A2 in the various aspects and/or embodiments describedherein.

In an embodiment, the amine having Structure A2 can be adi(aminomethyl)cycloalkane or a substituted di(aminomethyl)cycloalkane;alternatively, a di(aminomethyl)cycloalkane. The cycloalkane group ofthe di(aminomethyl)cycloalkane can be cyclobutane group, a substitutedcyclobutane group, a cyclopentane group, a substituted cyclopentanegroup, a cyclohexane group, a substituted cyclohexane group, acycloheptane group, a substituted cycloheptane group, a cyclooctanegroup, or a substituted cyclooctane group; alternatively, a cyclopentanegroup, a substituted cyclopentane group, a cyclohexane group, or asubstituted cyclohexane group; alternatively, a cyclobutane group or asubstituted cyclobutane group; alternatively, a cyclopentane group or asubstituted cyclopentane group; alternatively, a cyclohexane group or asubstituted cyclohexane group; alternatively, a cycloheptane group or asubstituted cycloheptane group; or alternatively, a cyclooctane group,or a substituted cyclooctane group. In some embodiments, the cycloalkanegroup of the di(aminomethyl)cycloalkane can be a cyclobutane group, acyclopentane group, a cyclohexane group, a cycloheptane group, or acyclooctane group; or alternatively, a cyclopentane group or acyclohexane group. In other embodiments, the cycloalkane group of thedi(aminomethyl)cycloalkane can be cyclopentane group; alternatively, asubstituted cyclopentane group; a cyclohexane group; or alternatively, asubstituted cyclohexane group.

In an embodiment, the amine having Structure A2 can be1,3-di(aminomethyl)cyclopentane, a substituted1,3-di(aminomethyl)cyclopentane, 1,3-di(aminomethyl)cyclohexane, asubstituted 1,3-di(aminomethyl)cyclohexane,1,4-di(aminomethyl)cyclohexane, or a substituted1,4-di(amino-methyl)cyclohexane; alternatively,1,3-di(aminomethyl)cyclopentane, 1,3-di(aminomethyl)cyclohexane, or1,4-di(aminomethyl)cyclohexane. In some embodiments, the amine havingStructure A2 can be 1,3-di(aminomethyl)cyclopentane or a substituted1,3-di(aminomethyl)cyclopentane; alternatively,1,3-di(aminomethyl)cyclohexane or a substituted1,3-di(aminomethyl)cyclohexane, 1,4-di(amino-methyl)cyclohexane, or asubstituted 1,4-di(aminomethyl)cyclohexane; alternatively,1,3-di(amino-methyl)cyclohexane or a substituted1,3-di(aminomethyl)cyclohexane; alternatively,1,4-di(amino-methyl)cyclohexane or a substituted1,4-di(aminomethyl)cyclohexane; alternatively,1,3-di(amino-methyl)cyclopentane; alternatively, a1,3-di(aminomethyl)cyclohexane; or alternatively, a1,4-di(aminomethyl)cyclohexane.

In an aspect, the amine having Structure A2 can be adi(aminomethyl)benzene, or a substituted di(aminomethyl)benzene;alternatively, a di(aminomethyl)benzene. In an embodiment, L¹ can be a1,2-di(aminomethyl)benzene, a substituted 1,2-di(aminomethyl)benzene, a1,3-di(aminomethyl)benzene, a substituted 1,3-di(aminomethyl)benzene, a1,4-di(aminomethyl)benzene, or a substituted1,4-di(amino-methyl)benzene; alternatively, a1,2-di(aminomethyl)benzene, a 1,3-di(aminomethyl)benzene, or a1,4-di(aminomethyl)benzene. In some embodiments, the amine havingStructure A2 can be a 1,2-di(aminomethyl)benzene or a substituted1,2-di(aminomethyl)benzene; alternatively, a 1,3-di(amino-methyl)benzeneor a substituted 1,3-di(aminomethyl)benzene; alternatively, a1,4-di(aminomethyl)-benzene or a substituted 1,4-di(aminomethyl)benzene;alternatively, a 1,2-di(aminomethyl)benzene; alternatively, a1,3-di(aminomethyl)benzene; or alternatively, a1,4-di(aminomethyl)benzene.

L¹ substituents for the general and specific substituteddi(methylene)cycloalkane groups and di(methylene)benzene groups aregenerally disclosed herein and can be utilized without limitation tofurther describe the general and specific substituteddi(aminomethyl)cycloalkanes and substituted di(aminomethyl)benzeneswhich can be utilized as the amine having structure A2 in the variousaspects and/or embodiments described herein.

In an aspect, the amine having Structure A2 can have Structure A10, A11,A12, A13, A14, A15, A16, A17, A18, A19, A20, A21, A22, or A23. In someembodiments, the amine having Structure A2 can have Structure A10, A11,or A12; alternatively, A13, A14, A15, or A16; alternatively, A17, A18,or A19; or alternatively, A20, A21, A22, or A23. In other embodiments,the amine having Structure A2 can have Structure A11 or A12;alternatively, A13 or A14; alternatively, A15 or A16; alternatively, A18or A19; alternatively, A20 or A21; or alternatively, A22 or A23. Infurther embodiments, the amine having Structure A2 can havealternatively, A10; alternatively, A11; alternatively, A12;alternatively, A13; alternatively, A14; alternatively, A15;alternatively, A16; alternatively, A17; alternatively, A18;alternatively, A19; alternatively, A20; alternatively, A21;alternatively, A22; or alternatively, A23.

TABLE 2 Diamines which can be utilized as the amine having Structure A2.

Structure A10

Structure A11

Structure A12

Structure A13

Structure A14

Structure A15

Structure A16

Structure A17

Structure A18

Structure A19

Structure A20

Structure A21

Structure A22

Structure A23

Aspects and embodiments for R^(1L)—R^(11L), R^(21L)—R^(31L),R^(21L′)—R^(31L′), R^(41L)—R^(51L), R^(41L′)—R^(51′), R^(62L)—R^(66L),R^(72L)—R^(76L), R^(72L′)—R^(76L′), R^(82L)—R^(86L), R^(82L′)—R^(86L′),and L^(a), are herein described for the linking group having Structures1L-14L. These aspects and embodiment can be utilized without limitationto describe the amine having Structures A9-A22 which can be utilized inthe various aspects and/or embodiments described herein.

In a non-limiting embodiment, the amine having Structure A2 can be1,4-diaminobenzene, 2,6-dimethyl-1,4-diaminobenzene,2,6-diethyl-1,4-diaminobenzene, 2,6-diisopropyl 1,4-diaminobenzene,2,6-di-tert-butyl-1,4-diaminobenzene, 2,5-dimethyl-1,4-diaminobenzene,2,5-diethyl-1,4-diaminobenzene, 2,5-diisopropyl-1,4-diaminobenzene,2,5-di-tert-butyl-1,4-diaminobenzene, or2,3,5,6-tetramethyl-1,4-diaminobenzene. In other non-limitingembodiments, the amine having Structure A2 can be 1,4-diaminobenzene,2,6-dimethyl-1,4-diaminobenzene, 2,6-diethyl-1,4-diaminobenzene,2,6-diisopropyl 1,4-diaminobenzene, or2,6-di-tert-butyl-1,4-diaminobenzene; alternatively,2,5-dimethyl-1,4-diaminobenzene, 2,5-diethyl-1,4-diaminobenzene,2,5-diisopropyl-1,4-diaminobenzene, or2,5-di-tert-butyl-1,4-diaminobenzene. In yet further non-limitingembodiments, the amine having Structure A2 can be 1,4-diaminobenzene;alternatively, 2,6-dimethyl-1,4-diaminobenzene; alternatively,2,6-diethyl-1,4-diaminobenzene; alternatively, 2,6-diisopropyl1,4-diaminobenzene; alternatively, 2,6-di-tert-butyl-1,4-diaminobenzene;alternatively, 2,5-dimethyl-1,4-diaminobenzene; alternatively,2,5-diethyl-1,4-diaminobenzene; alternatively,2,5-diisopropyl-1,4-diaminobenzene; alternatively,2,5-di-tert-butyl-1,4-diaminobenzene; or alternatively,2,3,5,6-tetramethyl-1,4-diaminobenzene.

In a non-limiting embodiment, the amine having Structure A2 can be3,3′-dimethyl-4,4′-bianiline, 3,3′-diethyl-4,4′-bianiline,3,3′-diisopropyl-4,4′-bianiline, 3,3′-di-tert-butyl-4,4′-bianiline,3,3′,5,5′-tetramethyl-4,4′-bianiline,3,3′,5,5′-tetraethyl-4,4′-bianiline,3,3′,5,5′-tetraisopropyl-4,4′-bianiline, or3,3′,5,5′-tetra-tert-butyl-4,4′-bianiline. In some embodiments, theamine having Structure A2 can be 3,3′-dimethyl-4,4′-bianiline,3,3′-diethyl-4,4′-bianiline, 3,3′-diisopropyl-4,4′-bianiline, or3,3′-di-tert-butyl-4,4′-bianiline; alternatively,3,3′,5,5′-tetramethyl-4,4′-bianiline,3,3′,5,5′-tetraethyl-4,4′-bianiline,3,3′,5,5′-tetraisopropyl-4,4′-bianiline, or3,3′,5,5′-tetra-tert-butyl-4,4′-bianiline. In other embodiments, theamine having Structure A2 can be 3,3′-dimethyl-4,4′-bianiline;alternatively, 3,3′-diethyl-4,4′-bianiline; alternatively,3,3′-diisopropyl-4,4′-bianiline; alternatively,3,3′-di-tert-butyl-4,4′-bianiline; alternatively,3,3′,5,5′-tetramethyl-4,4′-bianiline; alternatively,3,3′,5,5′-tetraethyl-4,4′-bianiline; alternatively,3,3′,5,5′-tetraisopropyl-4,4′-bianiline; or alternatively,3,3′,5,5′-tetra-tert-butyl-4,4′-bianiline.

In a non-limiting embodiment, the amine having Structure A2 can bebis(3-methyl-4-aminophenyl)methane, bis(3-ethyl-4-aminophenyl)methane,bis(3-isopropy-4-aminophenyl)methane,bis(3-tert-butyl-4-aminophenyl)methanebis(3,5-dimethyl-4-aminophenyl)methane,bis(3,5-diethyl-4-aminophenyl)methane,bis(3,5-diisopropy-4-aminophenyl)methane, orbis(3,5-di-tert-butyl-4-amino-phenyl)methane. In some embodiments, theamine having Structure A2 can be bis(3-methyl-4-amino-phenyl)methane,bis(3-ethyl-4-aminophenyl)methane, bis(3-isopropy-4-aminophenyl)methane,bis(3-tert-butyl-4-aminophenyl)methane; alternatively,bis(3,5-dimethyl-4-aminophenyl)methane,bis(3,5-diethyl-4-aminophenyl)methane,bis(3,5-diisopropy-4-aminophenyl)methane, orbis(3,5-di-tert-butyl-4-amino-phenyl)methane. In other embodiments, theamine having Structure A2 can be bis(3-methyl-4-amino-phenyl)methane;alternatively, bis(3-ethyl-4-aminophenyl)methane; alternatively,bis(3-isopropy-4-aminophenyl)methane; alternatively,bis(3-tert-butyl-4-aminophenyl)methane; alternatively,bis(3,5-dimethyl-4-aminophenyl)methane; alternatively,bis(3,5-diethyl-4-aminophenyl)methane; alternatively,bis(3,5-diisopropy-4-aminophenyl)methane; or alternatively,bis(3,5-di-tert-butyl-4-aminophenyl)-methane.

In a non-limiting embodiment, the amine having Structure A2 can bebis(3-methyl-4-amino-phenyl)ethane, bis(3-ethyl-4-aminophenyl)ethane,bis(3-isopropy-4-aminophenyl)ethane,bis(3-tert-butyl-4-aminophenyl)ethanebis(3,5-dimethyl-4-aminophenyl)ethane,bis(3,5-diethyl-4-aminophenyl)ethane,bis(3,5-diisopropy-4-aminophenyl)ethane, orbis(3,5-di-tert-butyl-4-aminophenyl)ethane. In some embodiments, theamine having Structure A2 can be bis(3-methyl-4-aminophenyl)ethane,bis(3-ethyl-4-aminophenyl)ethane, bis(3-isopropy-4-aminophenyl)ethane,bis(3-tert-butyl-4-aminophenyl)ethane; alternatively,bis(3,5-dimethyl-4-aminophenyl)ethane,bis(3,5-diethyl-4-aminophenyl)ethane,bis(3,5-diisopropyl-4-aminophenyl)ethane, orbis(3,5-di-tert-butyl-4-aminophenyl)ethane. In other embodiments, theamine having Structure A2 can be bis(3-methyl-4-aminophenyl)ethane;alternatively, bis(3-ethyl-4-aminophenyl)ethane; alternatively,bis(3-isopropy-4-aminophenyl)ethane; alternatively,bis(3-tert-butyl-4-aminophenyl)ethane; alternatively,bis(3,5-dimethyl-4-aminophenyl)ethane; alternatively,bis(3,5-diethyl-4-aminophenyl)ethane; alternatively,bis(3,5-diisopropy-4-aminophenyl)-ethane; or alternatively,bis(3,5-di-tert-butyl-4-aminophenyl)ethane. Generally, these substitutedbis(aminophenyl)ethanes can be bis-1,1-(aminophenyl)ethane orbis-1,2-(aminophenyl)ethane group; alternatively,bis-1,1-(aminophenyl)ethane; or alternatively,bis-1,2-(aminophenyl)ethane.

In an aspect, the amine having Structure A2 can have a structure whereinone or more of the carbon atoms attached to the nitrogen atom of the—NH₂ group can be a tertiary carbon atom or a quaternary carbon atom;alternatively, a tertiary carbon atom; or alternatively, a quaternarycarbon atom. In an embodiment, the amine having Structure A2 can have astructure wherein each carbon atom attached to a nitrogen atom of the—NH₂ group can be a tertiary carbon atom or a quaternary carbon atom;alternatively, a tertiary carbon atom; or alternatively, a quaternarycarbon atom.

In an embodiment, when a nitrogen atom of the amine group is attached toa ring atom (e.g. aminocycloalkane, aromatic amine, aminoarene,diamiocycloalkane, diaminoarene, bi(aminocyclyl),bis(aminocycloalkyl)methane, bis(aminocycloalkyl)ethane,bi(aminoanline), bis(aminophenyl)methane, bis(aminophenyl)ethane, or anamine having Structure A10-A23, among others), the amine can comprise atleast one substituent located on a carbon atom adjacent to the ringcarbon atom attached to the nitrogen atom of the amine group; oralternatively, the amine can comprise at least one substituent at eachcarbon atom adjacent to the ring carbon atom attached to the nitrogenatom of the amine group. In some embodiments, when the nitrogen atom ofthe amine group is attached to a ring atom(e.g. aminocycloalkane,aromatic amine, aminoarene, diamiocycloalkane, diaminoarene,bi(aminocyclyl), bis(aminocycloalkyl)methane,bis(aminocycloalkyl)ethane, bi(aminoanline), bis(aminophenyl)methane,bis(aminophenyl)ethane, or an amine having Structure A10-A23, amongothers), the amine can consist of one substituent located on a carbonatom adjacent to the ring carbon atom attached to the nitrogen atom ofthe amine group. In some embodiments, when the nitrogen atom of theamine group is attached to a ring atom (e.g. aminocycloalkane, aromaticamine, aminoarene, diamio-cycloalkane, diaminoarene, bi(aminocyclyl),bis(aminocycloalkyl)methane, bis(aminocycloalkyl)ethane,bi(aminoanline), bis(aminophenyl)methane, bis(aminophenyl)ethane, or anamine having Structure A10-A23, among others), the amine can compriseonly one substituent located on the carbon atom adjacent to the ringcarbon atom attached to the nitrogen atom of the amine group; oralternatively, the amine can comprise only one substituent located oneach carbon atom adjacent to the ring carbon atom attached to thenitrogen atom of the amine group. In yet other embodiments, when thenitrogen atom of the amine is attached to a ring atom (e.g.aminocycloalkane, aromatic amine, aminoarene, diamiocycloalkane,diaminoarene, bi(aminocyclyl), bis(aminocycloalkyl)methane,bis(aminocycloalkyl)ethane, bi(amino-anline), bis(aminophenyl)methane,bis(aminophenyl)ethane, or an amine having Structure A10-A23, amongothers), the amine can consist of only one substituent located on acarbon atom adjacent to the ring carbon atom attached to the nitrogenatom of the amine group.

In an aspect, the amine having Structure A3 can be1-(2-aminoethyl)pyrrolidine, 1-(2-amino-ethyl)morpholine,1-(2-aminoethyl)piperidine, 2-(2-aminoethyl)piperidine,2-(2-aminoethyl)pyrrolidine, N,N-dimethylethylenediamine,N,N-diethylethylenediamine, N,N-diphenylethylenediamine,2-amino-thiazole, 2-(aminomethyl)pyridine, 2-(2-aminoethyl)pyridine,2-(diphenylphosphino)ethylamine, 3-(diphenylphosphino)propylamine,2-(2-aminoethyl)furan, 2-(aminomethyl)furan, 2-(2-aminoethyl)-thiophene,2-(aminomethyl)thiophene, 2-aminoethyl-(phenyl)sulfide,2-phenoxyethylamine, 2-methoxy-ethylamine, 2-ethoxyethylamine, or2-isopropoxyethylamine. In some embodiments, the amine having StructureA3 can be N,N-dimethylethylenediamine, N,N-diethylethylenediamine,N,N-diphenylethylene-diamine, 1-(2-aminoethyl)morpholine,2-aminothiazole, 2-(aminomethyl)pyridine, 2-(2-aminoethyl)-pyridine,2-(diphenylphosphino)ethylamine, 3-(diphenylphosphino)propylamine,2-aminoethyl-(phenyl)-sulfide, 2-phenoxyethylamine, 2-methoxyethylamine,2-ethoxyethylamine, or 2-isopropoxyethylamine In yet other embodiments,the amine having Structure A3 can be N,N-dimethylethylenediamine orN,N-diethylethylenediamine; alternatively, N,N-diphenylethylenediamine,2-(diphenylphosphino)ethylamine, 3-(diphenylphosphino)propylamine;alternatively, 2-(aminomethyl)pyridine, 2-(2-aminoethyl)pyridine; oralternatively, 2-phenoxyethylamine, 2-methoxyethylamine,2-ethoxyethylamine, or 2-isopropoxyethyl-amine. In further embodiments,the amine having Structure A3 can be N,N-dimethylethylenediamine;alternatively, N,N-diethylethylenediamine; alternatively,N,N-diphenylethylenediamine; alternatively,2-(diphenylphosphino)ethylamine; alternatively,3-(diphenylphosphino)propylamine; alternatively, 2-aminothiazole;alternatively, 2-(aminomethyl)pyridine; alternatively,2-(2-aminoethyl)pyridine; or alternatively,2-aminoethyl-(phenyl)sulfide.

In a non-limiting embodiment, the amine having Structure A3 can be2-aminoethyl-(4-methyl-phenyl) sulfide,2-aminoethyl-(4-ethylphenyl)sulfide,2-aminoethyl-(4-isopropylphenyl)sulfide,2-amin-oethyl-(4-tert-butylphenyl)sulfide. In some non-limitingembodiments, the amine having Structure A3 can be2-aminoethyl-(4-chlorophenyl)sulfide; alternatively,2-aminoethyl-(4-methylphenyl)sulfide; alternatively, a2-aminoethyl-(4-ethylphenyl)sulfide; alternatively,2-aminoethyl-(4-isopropylphenyl)-sulfide; or alternatively,2-aminoethyl-(4-tert-butylphenyl)sulfide. In other non-limitingembodiments, the amine having Structure A3 can be2-aminoethyl-(2,6-dimethylphenyl)sulfide; or alternatively,2-aminoethyl-(3,5-dimethylphenyl)sulfide. In yet other non-limitingembodiments, the amine having Structure A3 can be2-aminoethyl-(4-methoxyphenyl)sulfide,2-aminoethyl-(4-ethoxyphenyl)sulfide,2-aminoethyl-(4-isopropoxyphenyl)sulfide, or2-aminoethyl-(4-tert-butoxyphenyl)sulfide. In further embodiments, theamine having Structure A3 can be 2-aminoethyl-(4-methoxyphenyl)sulfide;alternatively, 2-aminoethyl-(4-ethoxyphenyl)sulfide; alternatively,2-aminoethyl-(4-isopropoxyphenyl)-sulfide; or alternatively,2-aminoethyl-(4-tert-butoxyphenyl)sulfide.

In an aspect, D′ of the amine having Structure A4 can be any D′described herein. D′ is described herein as a feature of theN²-phosphinyl amidine metal salt complexes utilized in various aspectsof this disclosure. Since the amines having structure A3 can be utilizedto prepare embodiments of the N²-phospinyl amidine compounds havingStructure NP4, the aspects and embodiments of D′ can utilized withoutlimitation to further describe the amines having Structures A4.

Within this disclosure, nitriles can be used to ultimately prepare theN²-phosphinyl amidine compounds and/or the N²-phosphinyl amidine metalsalt complexes utilized in various aspects of this disclosure. Invarious embodiments, nitriles which can be utilized can have StructureN¹, N², or N3; alternatively, N1; alternatively, N2; or alternatively,N3.

R²—C≡N N≡C—L²—C≡N D² C≡N)_(r) Structure N1 Structure N2 Structure N3

compounds having Structures NP1—NP5 and are described herein. Sincenitriles N1-N3 are utilized to ultimately prepare embodiments of theN²-phospinyl amidine compounds having Structures NP1—NP5, R², L², D²,and r within nitrile Structures N1-N3 are independently described asfeatures of the N²-phospinyl amidine compounds Structures NP1-NP10,NP11, NP13, NP15, NP16, NP18, and/or NP20. Since nitrile havingStructures N1-N3 are ultimately utilized to prepare embodiments ofN²-phospinyl amidine compounds having Structures NP1-NP10, NP11, NP13,NP15, NP16, NP18, and/or NP20, the R², L², D², and r descriptions forthe N²-phospinyl amidine compounds may be utilized without limitation tofurther describe the amine Structures N1-N3.

In an aspect, the nitrile having Structure N1 can be acetonitrile,propanenitrile, a butanenitrile, a pentanenitrile, a hexanenitrile, aheptanenitrile, an octanenitrile, a nonane nitrile, a decanenitrile, anundecanenitrile, a dodecanenitrile, a tridecanenitrile, atetradecanenitrile, a pentadecanenitrile, a hexadecanenitrile, aheptadecane, an octadecanenitrile, a nonadecanenitrile, or an eicosanenitrile; or alternatively, acetonitrile, propanenitrile, abutanenitrile, a pentanenitrile, a hexanenitrile, a heptane nitrile, anoctanenitrile, a nonane nitrile, a decanenitrile, or an undecanenitrile.In some embodiments, the nitrile having Structure N1 can beacetonitrile, propanenitrile, n-butanenitrile, 2-methylpropanenitrile,n-pentanenitrile, 3-methylbutanenitrile, 2-methyl-butanenitrile,2,2-dimethylpropanenitrile, n-hexanenitrile, 3-methylbutanenitrile, or3,3-dimethylbutanenitrile; alternatively, acetonitrile, propanenitrile,2-methylpropanenitrile, 2,2-dimethylpropanenitrile, or3,3-dimethylbutanenitrile; alternatively, acetonitrile; alternatively,propanenitrile; alternatively, n-butanenitrile; alternatively,n-pentanenitrile; alternatively, 2-methylpropanenitrile; alternatively,2,2-dimethylpropanenitrile; or alternatively, 3,3-dimethylbutanenitrile.

In an aspect, the nitrile having Structure N1 can becyclobutylcarbonitrile, a substituted cyclobutylcarbonitrile,cyclopentylcarbonitrile, a substituted cyclopentylcarbonitrile,cyclohexyl-carbonitrile, a substituted cyclohexylcarbonitrile,cycloheptylcarbonitrile, a substituted cycloheptyl-carbonitrile,cyclooctylcarbonitrile, or a substituted cyclooctylcarbonitrile. In someembodiments, the nitrile can be cyclopentylcarbonitrile, a substitutedcyclopentylcarbonitrile, cyclohexylcarbonitrile, a substitutedcyclohexylcarbonitrile. In other embodiments, the nitrile can becyclobutylcarbonitrile or a substituted cyclobutylcarbonitrile;alternatively, cyclopentylcarbonitrile or a substitutedcyclopentyl-carbonitrile; alternatively, cyclohexylcarbonitrile or asubstituted cyclohexylcarbonitrile; alternatively,cycloheptylcarbonitrile or a substituted cycloheptylcarbonitrile; oralternatively, cyclooctylcarbonitrile, or a substitutedcyclooctylcarbonitrile. In further embodiments, the nitrile can becyclopentylcarbonitrile; alternatively, a substitutedcyclopentylcarbonitrile; cyclohexylcarbonitrile; or alternatively, asubstituted cyclohexylcarbonitrile. Substituents and substituentspatterns for the R² cycloalkyl groups are described herein and can beutilized without limitation to further describe the substitutedcycloalkylcarbonitriles which can be utilized in aspects and/orembodiments described herein.

In an aspect, the nitrile having Structure N1 can have Structure N4. TheR^(21c), R^(22c), R^(23c), R^(24c), and R^(25c) substituents,substituent patterns, and n for the R² group having Structure N4 aredescribed

herein and can be utilized without limitation to describe the nitrilehaving Structure N4 which can be utilized in the various aspects and/orembodiments described herein.

In an embodiment, the nitrile having Structure N1 can be benzonitrile ora substituted benzonitrile. In some embodiments, the nitrile havingStructure N1 can be benzonitrile; or alternatively, a substitutedbenzonitrile. In an embodiment, the substituted benzonitrile can be a2-substituted benzonitrile, a 3-substituted benzonitrile, a4-substituted benzonitrile, a 2,4-disubstituted benzonitrile, a2,6-disubstituted benzonitrile, a 3,5-disubstituted benzonitrile, or a2,4,6-trisubstituted benzonitrile. In other embodiments, the substitutedbenzonitrile can be a 2-substituted benzonitrile, a 4-substitutedbenzonitrile, a 2,4-disubstituted benzonitrile, or a 2,6-disubstitutedbenzonitrile; alternatively, a 3-substituted benzonitrile or a3,5-disubstituted benzonitrile; alternatively, a 2-substitutedbenzonitrile or a 4-substituted benzonitrile; alternatively, a2,4-disubstituted benzonitrile or a 2,6-disubstituted benzo-nitrile;alternatively, a 2-substituted benzonitrile; alternatively, a3-substituted benzonitrile; alternatively, a 4-substituted benzonitrile;alternatively, a 2,4-disubstituted benzonitrile; alternatively, a2,6-disubstituted benzonitrile; alternatively, a, 3,5-disubstitutedbenzonitrile; or alternatively, a 2,4,6-trisubstituted benzonitrile.Substituents for the R² phenyl groups are generally disclosed herein andcan be utilized without limitation to further describe the substitutedbenzonitriles which can be utilized in the various aspects and/orembodiments described herein.

In an aspect, the nitrile having Structure N1 can have Structure N5. TheR²², R²³, R²⁴, R²⁵, and R²⁶ substituents and substituent patterns forthe R² group having Structure G4 are described

herein and can be utilized without limitation to describe the nitrilehaving Structure N5 which can be utilized in the various aspects and/orembodiments described herein.

In an embodiment, the nitrile having Structure N1 can bephenylacetonitrile, a substituted phenylacetonitrile,2-phenylpropanenitrile, a substituted 2-phenylpropanenitrile,3-phenylpropanenitrile, or a substituted 3-phenylpropanenitrile. In someembodiments, the nitrile having Structure N1 can be phenylacetonitrileor a substituted phenylacetonitrile; alternatively,2-phenylpropanenitrile or a substituted 2-phenylpropanenitrile;alternatively, 3-phenylpropanenitrile or a substituted3-phenyl-propanenitrile; or alternatively, phenylacetonitrile,2-phenylpropanenitrile, or 3-phenylpropanenitrile. In other embodiments,the nitrile having Structure N1 can be phenylacetonitrile;alterantively, a substituted phenylacetonitrile; alterantively,2-phenylpropanenitrile; alterantively, a substituted2-phenylpropane-nitrile; alterantively, 3-phenylpropanenitrile; oralterantively, a substituted 3-phenylpropanenitrile. Substituents for R²benzyl group, 1-phenyleth-1-yl, and/or 2-phenyleth-1-yl groups aregenerally disclosed herein and can be utilized without limitation tofurther describe the substituted phenylaceto-nitriles,2-phenylpropanenitriles, and/or 3-phenylpropanenitriles which can beutilized in the various aspects and/or embodiments described herein.

In an aspect, the nitrile having Structure N1 can be apyridinecarbonitrile, a substituted pyridinecarbonitrile, afurancarbonitrile, a substituted furancarbonitrile, athiophenecarbonitrile, or a substituted thiophenecarbonitrile. In anembodiment, the nitrile having Structure N1 can be apyridine-carbonitrile or a substituted pyridinecarbonitrile;alternatively, a furancarbonitrile or a substituted furancarbonitrile;or alternatively, a thiophenecarbonitrile, or a substitutedthiophenecarbonitrile. In some embodiments, the nitrile having StructureN1 can be a pyridinecarbonitrile, a furancarbonitrile, or athiophenecarbonitrile. In other embodiments, the nitrile havingStructure N1 can be a pyridine-carbonitrile; alternatively, asubstituted pyridinecarbonitrile; alternatively, a furancarbonitrile;alternatively, a substituted furancarbonitrile; alternatively, athiophenecarbonitrile; or alternatively, a substitutedthiophenecarbonitrile.

In an embodiment, the pyridinecarbonitrile (or substitutedpyridinecarbonitrile) can be 2-pyridinecarbonitrile, a substituted2-pyridinecarbonitrile, 3-pyridinecarbonitrile, a substituted3-pyridinecarbonitrile, 4-pyridinecarbonitrile, or a substituted4-pyridinecarbonitrile; alternatively, 2-pyridinecarbonitrile,3-pyridinecarbonitrile, or 4-pyridinecarbonitrile. In some embodiments,the pyridinecarbonitrile (or substituted pyridinecarbonitrile) can be2-pyridinecarbonitrile or a substituted 2-pyridinecarbonitrile;alternatively, 3-pyridinecarbonitrile or a substituted3-pyridinecarbonitrile; alternatively, 4-pyridinecarbonitrile, or asubstituted 4-pyridinecarbonitrile; alternatively,2-pyridine-carbonitrile; alternatively, a substituted2-pyridinecarbonitrile; alternatively, 3-pyridinecarbonitrile;alternatively, a substituted 3-pyridinecarbonitrile; alternatively,4-pyridinecarbonitrile; or alternatively, a substituted4-pyridinecarbonitrile. In an embodiment, the pyridinecarbonitrile (orsubstituted pyridine-carbonitrile) can be a2-substituted-3-pyridinecarbonitrile, a4-substituted-3-pyridinecarbonitrile, a5-substituted-3-pyridinecarbonitrile, a6-substituted-3-pyridinecarbonitrile, a2,4-disubstituted-3-pyridine-carbonitrile, a2,6-disubstituted-3-pyridinecarbonitrile, or a2,4,6-trisubstituted-3-pyridinecarbonitrile; alternatively, a2-substituted-3-pyridinecarbonitrile, a4-substituted-3-pyridinecarbonitrile, a6-substituted-3-pyridinecarbonitrile; alternatively, a2,4-disubstituted-3-pyridinecarbonitrile or a2,6-disubstituted-3-pyridinecarbonitrile; alternatively, a2-substituted-3-pyridinecarbonitrile; alternatively, a4-substituted-3-pyridinecarbonitrile; alternatively, a5-substituted-3-pyridinecarbonitrile; alternatively, a6-substituted-3-pyridinecarbonitrile; alternatively, a2,4-disubstituted-3-pyridinecarbonitrile; alternatively, a2,6-disubstituted-3-pyridinecarbonitrile; or alternatively, a2,4,6-trisubstituted-3-pyridine-carbonitrile. In an embodiment, thepyridinecarbonitrile (or substituted-pyridinecarbonitrile) can be a2-substituted-4-pyridinecarbonitrile, a3-substituted-4-pyridinecarbonitrile, a5-substituted-4-pyridine-carbonitrile, a6-substituted-4-pyridinecarbonitrile, a2,6-disubstituted-4-pyridinecarbonitrile, or a3,5-disubstituted-4-pyridinecarbonitrile; alternatively,2-substituted-4-pyridinecarbonitrile, a6-substituted-4-pyridinecarbonitrile; alternatively, a3-substituted-4-pyridinecarbonitrile or a5-substituted-4-pyridine-carbonitrile; alternatively, a2-substituted-4-pyridinecarbonitrile; alternatively, a3-substituted-4-pyridine-carbonitrile; alternatively, a5-substituted-4-pyridinecarbonitrile; alternatively, a6-substituted-4-pyridine-carbonitrile; alternatively, a2,6-disubstituted-4-pyridinecarbonitrile; or alternatively, a3,5-disubstituted-4-pyridinecarbonitrile. Substituents for the R²pyridinyl groups are generally disclosed herein and can be utilizedwithout limitation to further describe the substitutedpyridinecarbonitriles which can be utilized in the various aspectsand/or embodiments described herein.

In an embodiment, the furancarbonitrile (or substitutedfurancarbonitrile) can be 2-furan-carbonitrile, a substituted2-furancarbonitrile, a 3-furancarbonitrile, or a substituted3-furancarbonitrile; alternatively, a 2-furancarbonitrile or a3-furancarbonitrile. In some embodiments, the furancarbonitrile (orsubstituted furancarbonitrile) can be a 2-furancarbonitrile or asubstituted 2-furancarbonitrile; alternatively, a 3-furancarbonitrile ora substituted 3-furancarbonitrile; alternatively, a 2-furancarbonitrile;alternatively, a substituted 2-furancarbonitrile; alternatively, a3-furancarbonitrile; or alternatively, a substituted3-furancarbonitrile. In an embodiment, the furancarbonitrile (orsubstituted furancarbonitrile) can be a2-substituted-3-furancarbonitrile, a 4-substituted-3-furancarbonitrile,or a 2,4-disubstituted-3-furancarbonitrile; alternatively, a2-substituted-3-furancarbonitrile; alternatively, a4-substituted-3-furancarbonitrile; or alternatively, a2,4-disubstituted-3-furancarbonitrile. Substituents for the R² furylgroups are generally disclosed herein and can be utilized withoutlimitation to further describe the substituted furancarbonitriles whichcan be utilized in the various aspects and/or embodiments describedherein.

In an embodiment, the thiophenenitrile (or substituted thiophenenitrile)can be a 2-thiophenecarbonitrile, a substituted 2-thiophenecarbonitrile,a 3-thiophenecarbonitrile, or a substituted 3-thiophenecarbonitrile;alternatively, a 2-thiophenecarbonitrile or a 3-thiophenecarbonitrile.In some embodiments, the thiophenenitrile (or substitutedthiophenenitrile) group can be a 2-thiophenecarbonitrile or asubstituted 2-thiophenecarbonitrile; alternatively, a3-thiophenecarbonitrile or a substituted 3-thiophenecarbonitrile;alternatively, a 2-thiophenecarbonitrile; alternatively, a substituted2-thiophene-carbonitrile; alternatively, a 3-thiophenecarbonitrile; oralternatively, a substituted 3-thiophene-carbonitrile. In an embodiment,the thiophenenitrile (or substituted thiophenenitrile) can be a2-substituted-3-thiophenecarbonitrile, a4-substituted-3-thiophenecarbonitrile, or a2,4-disubstituted-3-thiophenecarbonitrile; alternatively, a2-substituted-3-thiophenecarbonitrile; alternatively, a4-substituted-3-thiophenecarbonitrile; or alternatively, a2,4-disubstituted-3-thiophenecarbonitrile. Substituents for the R²thienyl groups are generally disclosed herein and can be utilizedwithout limitation to further describe the substitutedthiophenecarbonitriles which can be utilized in the various aspectsand/or embodiments described herein.

In a non-limiting embodiment, the nitrile having Structure N1 can bebenzonitrile, a 2-alkylbenzonitrile, a 3-alkylbenzonitrile, a4-alkylbenzonitrile, a 2,4-dialkylbenzonitrile a2,6-dialkyl-benzonitrile, a 3,5-dialkylbenzonitrile, or a2,4,6-trialkylbenzonitrile; alternatively, a 2-alkylbenzonitrile, a4-alkylbenzonitrile, a 2,4-dialkylbenzonitrile, a2,6-dialkylbenzonitrile, or a 2,4,6-trialkylbenzonitrile; alternatively,a 2-alkylbenzonitrile or a 4-alkylbenzonitrile; alternatively, a2,4-dialkylbenzonitrile or a 2,6-dialkylbenzonitrile; alternatively, a3-alkylbenzonitrile or a 3,5-dialkylbenzonitrile; alternatively, a2-alkylbenzonitrile or a 2,6-dialkylbenzonitrile; alternatively, a2-alkylbenzonitrile; alternatively, a 3-alkyl-benzonitrile;alternatively, a 4-alkylbenzonitrile; alternatively, a2,4-dialkylbenzonitrile; alternatively, a 2,6-dialkylbenzonitrile;alternatively, a 3,5-dialkylbenzonitrile; or alternatively, a2,4,6-trialkylbenzo-nitrile. In another non-limiting embodiment, thenitrile having Structure N1 can be benzonitrile, a 2-alkoxybenzonitrile,a 3-alkoxybenzonitrile, a 4-alkoxybenzonitrile, or3,5-dialkoxybenzonitrile; alternatively, a 2-alkoxybenzonitrile or a4-alkoxybenzonitrile; alternatively, a 3-alkoxybenzonitrile or3,5-dialkoxybenzonitrile; alternatively, a 2-alkoxybenzonitrile;alternatively, a 3-alkoxybenzonitrile; alternatively, a4-alkoxybenzonitrile; or alternatively, a 3,5-dialkoxybenzonitrile. Inother non-limiting embodiments, the nitrile having Structure N1 can bebenzonitrile, a 2-halobenzonitrile, a 3-halobenzo-nitrile, a4-halobenzonitrile, a 2,6-dihalobenzonitrile, or a3,5-dialkylbenzonitrile; alternatively, a 2-halobenzonitrile, a4-halobenzonitrile, or a 2,6-dihalobenzonitrile; alternatively, a2-halobenzonitrile or a 4-halobenzonitrile; alternatively, a3-halobenzonitrile or a 3,5-dihalobenzonitrile; alternatively, a2-halo-benzonitrile; alternatively, a 3-halobenzonitrile; alternatively,a 4-halobenzonitrile; alternatively, a 2,6-dihalobenzonitrile; oralternatively, a 3,5-dialkylbenzonitrile.

Halides, alkyl group substituents, and alkoxy group substituents areindependently described herein and can be utilized, without limitation,to further describe the alkylbenzonitriles, dialkyl-benzonitriles,trialkylbenzonitriles, alkoxybenzonitriles, dialkoxybenzonitriles,halobenzonitriles, or dihalobenzonitriles which can be utilized in thevarious aspects and/or embodiments described herein. Generally, thehalides, alkyl substituents, or alkoxy substituents of thedialkylbenzonitriles, trialkyl-benzonitriles, dialkoxybenzonitriles, ordihalobenzonitriles can be the same; or alternatively, the halo, alkylsubstituents, or alkoxy substituents of alkylbenzonitriles,dialkylbenzonitriles, trialkylbenzonitriles, dialkoxybenzonitriles, ordihalobenzonitriles can be different.

In a non-limiting embodiment, the nitrile having Structure N1 can be2-methylbenzonitrile, 2-ethylbenzonitrile, 2-isopropylbenzonitrile,2-tert-butylbenzonitrile, 4-methylbenzonitrile, 4-ethylbenzo-nitrile,4-isopropylbenzonitrile, or 4-tert-butylbenzonitrile; alternatively,2-methylbenzonitrile, 2-ethylbenzonitrile, 2-isopropylbenzonitrile, or2-tert-butylbenzonitrile; alternatively, 4-methylbenzonitrile,4-ethylbenzonitrile, 4-isopropylbenzonitrile, or4-tert-butylbenzonitrile; alternatively, 2-methylbenzonitrile;alternatively, 2-ethylbenzonitrile; alternatively,2-isopropylbenzonitrile; alternatively, 2-tert-butylbenzonitrile;alternatively, 4-methylbenzonitrile; alternatively, 4-ethylbenzonitrile;alternatively, 4-isopropylbenzonitrile; or alternatively,4-tert-butylbenzonitrile. In another non-limiting embodiment, thenitrile having Structure N1 can be a 2-methoxybenzonitrile,2-ethoxybenzonitrile, 2-isopropoxybenzonitrile,2-tert-butoxybenzonitrile, 4-methoxybenzonitrile, 4-ethoxybenzonitrile,4-isopropoxybenzonitrile, or 4-tert-butoxybenzonitrile; alternatively,2-methoxybenzonitrile, 2-ethoxy-benzonitrile, 2-isopropoxybenzonitrile,or 2-tert-butoxybenzonitrile; alternatively, 4-methoxybenzonitrile,4-ethoxybenzonitrile, 4-isopropoxybenzonitrile, or4-tert-butoxybenzonitrile; alternatively, 2-methoxy-benzonitrile;alternatively, 2-ethoxybenzonitrile; alternatively,2-isopropoxybenzonitrile; alternatively, 2-tert-butoxybenzonitrile;alternatively, 4-methoxybenzonitrile; alternatively,4-ethoxybenzonitrile; alternatively, 4-isopropoxybenzonitrile; oralternatively, 4-tert-butoxybenzonitrile. In other non-limitingembodiments, the nitrile having Structure N1 can be2-fluorobenzonitrile, 2-chlorobenzonitrile, 3-fluoro-benzonitrile,3-chlorobenzonitrile, 4-fluorobenzonitrile, 4-chlorobenzonitrile,3,5-difluorobenzonitrile, or 3,5-dichlorobenzonitrile; alternatively,2-fluorobenzonitrile or 2-chlorobenzonitrile; alternatively,3-fluorobenzonitrile or 3-chlorobenzonitrile; alternatively,4-fluorobenzonitrile or 4-chlorobenzonitrile; alternatively,3,5-difluorobenzonitrile or 3,5-dichlorobenzonitrile; alternatively,3-fluorobenzonitrile, 3-chlorobenzonitrile, 3,5-difluorobenzonitrile or3,5-dichlorobenzonitrile; alternatively, 3-fluorobenzo-nitrile or3,5-difluorobenzonitrile; alternatively, 2-fluorobenzonitrile;alternatively, 2-chlorobenzonitrile; alternatively,3-fluorobenzonitrile; alternatively, 3-chlorobenzonitrile;alternatively, 4-fluorobenzonitrile; alternatively,4-chlorobenzonitrile; alternatively, 3,5-difluorobenzonitrile; oralternatively, 3,5-dichloro-benzonitrile.

In an aspect, L² of the nitrile having Structure N2 can be any L²described herein. L² is described herein as a feature of theN²-phosphinyl amidine metal salt complexes utilized in various aspectsand/or embodiments of this disclosure. Since the nitriles havingstructure N2 can be utilized to prepare embodiments of the N²-phospinylamidine compounds having Structure NP2, the aspects and/or embodimentsof L² can utilized without limitation to further describe the nitrileshaving Structures N2.

In an embodiment, the nitrile having Structure N2 can be oxanitrile,propanedinitrile, a butanedinitrile, a pentanedinitrile, ahexanedinitrile, a heptanedinitrile, an octanedinitrile, anonane-dinitrile, a decanedinitrile, an undecanedinitrile, adodecanedinitrile, a tridecanedinitrile, a tetradecane-dinitrile, apentadecanedinitrile, a hexadecanedinitrile, a heptadecanedinitrile, anoctadecanedinitrile, a nonadecanedinitrile, an eicosanedinitrile, or aheneicosanedinitrile; or alternatively, propanedinitrile, abutanedinitrile, a pentanedinitrile, a hexanedinitrile, aheptanedinitrile, an octanedinitrile, a nonaedinitrile, adecanedinitrile, an undecanedinitrile, a dodecanedinitrile. In someembodiments, the nitrile having Structure N2 can be propanedinitrile, abutanedinitrile, a pentanedinitrile, a hexanedinitrile, or aheptane-dinitrile. In other embodiments, the amine having Structure N2can be oxanitrile; alternatively, propane-dinitrile; alternatively, abutanedinitrile; alternatively, a pentanedinitrile; alternatively, ahexanedinitrile; alternatively, a heptanedinitrile; alternatively, anoctanedinitrile; alternatively, a noanedinitrile; alternatively, adecanedinitrile; alternatively, an undecanedinitrile; alternatively, adodecanedinitrile; alternatively, a tridecanedinitrile; alternatively, atetradecanedinitrile; alternatively, a pentadecane-dinitrile;alternatively, a hexadecanedinitrile; alternatively, aheptadecanedinitrile; alternatively, an octadecanedinitrile;alternatively, a nonadecanedinitrile; alternatively, aneicosanedinitrile; or alternatively, a heneicosanedinitrile. In someembodiments, the nitrile having Structure N2 can be propanedinitrile,n-butanedinitrile, 2-methylpropanedinitrile, n-pentanedinitrile,2-methylbutanedinitrile, n-hexanedinitrile, 2,3-dimethylbutanedinitrile,n-heptanedinitrile, 2,2-dimethylpentanedinitrile, n-octane-dinitrile, or2,2,3,3-tetramethylbutanedinitrile; propanedinitrile, n-butanedinitrile,n-pentanedinitrile, n-hexanedinitrile, n-heptanedinitrile, orn-octanedinitrile; alternatively, propanedinitrile; alternatively,n-butanedinitrile; alternatively, 2-methylpropanedinitrile;alternatively, n-pentanedinitrile; alternatively,2-methylbutanedinitrile; alternatively, n-hexanedinitrile;alternatively, 2,3-dimethylbutanedinitrile; alternatively,n-heptanedinitrile; alternatively, 2,2-dimethylpentanedinitrile;alternatively, n-octanedinitrile; or alternatively,2,2,3,3-tetramethylbutanedinitrile.

In an aspect, the nitrile having Structure N2 can have the formulaN≡C—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—C≡N. R^(1a), R^(2a), R^(3a),R^(4a), and t are described herein as embodiments of an L² group havingstructure —CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—. The descriptions ofR^(1a), R^(2a), R^(3a), R^(4a) and t can be utilized without limitationto further describe the nitriles having the formulaN≡C—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—C≡N which can be utilized in thevarious aspects and/or embodiments described herein.

In an embodiment, the nitrile having Structure N2 can be acyclobutanedicarbonitrile, a substituted cyclobutanedicarbonitrile, acyclopentanedicarbonitrile, a substituted cyclopentanedicarbonitrile, acyclohexanedicarbonitrile, a substituted cyclohexanedicarbonitrile, acycloheptanedicarbonitrile, a substituted cycloheptanedicarbonitrile, acyclooctanedicarbonitrile, or a substituted cyclooctanedicarbonitrile.In some embodiments, the nitrile having Structure N2 can be acyclopentanedicarbonitrile, a substituted cyclopentanedicarbonitrile, acyclohexanedicarbonitrile, a substituted cyclohexanedicarbonitrile. Inother embodiments, the nitrile having Structure N2 can be acyclobutanedicarbonitrile or a substituted cyclobutanedicarbonitrile;alternatively, a cyclopentane-dicarbonitrile or a substitutedcyclopentanedicarbonitrile; alternatively, a cyclohexanedicarbonitrileor a substituted cyclohexanedicarbonitrile; alternatively, acycloheptanedicarbonitrile or a substituted cycloheptanedicarbonitrile;or alternatively, a cyclooctanedicarbonitrile, or a substitutedcyclooctane-dicarbonitrile. In further embodiments, the nitrile havingStructure N2 can be a cyclopentane-dicarbonitrile; alternatively, asubstituted cyclopentanedicarbonitrile; a cyclohexanedicarbonitrile; oralternatively, a substituted cyclohexanedicarbonitrile.

In an embodiment, the nitrile having Structure N2 can be1,3-cyclopentanedicarbonitrile, a substituted1,3-cyclopentanedicarbonitrile, 1,3-cyclohexanedicarbonitrile, asubstituted 1,3-cyclohexane-dicarbonitrile,1,4-cyclohexanedicarbonitrile, or a substituted1,4-cyclohexanedicarbonitrile; alternatively,1,3-cyclopentanedicarbonitrile, 1,3-cyclohexanedicarbonitrile, or1,4-cyclohexanedicarbonitrile. In some embodiments, the nitrile havingStructure N2 can be 1,3-cyclopentanedicarbonitrile or a substituted1,3-cyclopentanedicarbonitrile; alternatively,1,3-cyclohexanedicarbonitrile a substituted1,3-cyclohexane-dicarbonitrile, 1,4-cyclohexanedicarbonitrile, or asubstituted 1,4-cyclohexanedicarbonitrile; alternatively,1,3-cyclohexanedicarbonitrile or a substituted1,3-cyclohexanedicarbonitrile; alternatively,1,4-cyclohexanedicarbonitrile or a substituted1,4-cyclohexanedicarbonitrile; alternatively,1,3-cyclopentanedicarbonitrile; alternatively,1,3-cyclohexanedicarbonitrile; or alternatively,1,4-cyclohexanedicarbonitrile.

L² substituents and substituent patterns for substituted L² cycloalkanegroups are generally disclosed herein and can be utilized withoutlimitation to further describe the substitutedcycloalkanedicarbonitriles which can be utilized as the nitrile havingStructure N2 in the various aspects and/or embodiments described herein.

In an aspect, the nitrile having Structure N2 can be abi(cyclylcarbonitrile), a substituted bi(cyclylcarbonitrile), abis(cyclylcarbonitrile)methane, a substitutedbis(cyclylcarbonitrile)methane, a bis(cyclylcarbonitrile)ethane, or asubstituted bis(cyclylcarbonitrile)ethane; or alternatively, abis(cyclyl-carbonitrile), a bis(cyclylcarbonitrile)methane, or abis(cyclylcarbonitrile)ethane. In an embodiment, the nitrile havingStructure N2 can be a bi(cyclylcarbonitrile) or a substitutedbi(cyclylcarbonitrile); alternatively, a bis(cyclylcarbonitrile)methaneor a substituted bis(cyclylcarbonitrile)methane; or alternatively, abis(cyclylcarbonitrile)ethane or a substitutedbis(cyclylcarbonitrile)ethane. In some embodiments, the nitrile havingStructure N2 can be a bi(cyclylcarbonitrile); alternatively, asubstituted bi(cyclylcarbonitrile); alternatively, abis(cyclylcarbonitrile)methane; alternatively, a substitutedbis(cyclylcarbonitrile)methane; alternatively, abis(cyclylcarbonitrile)ethane; or alternatively, a substitutedbis(cyclylcarbonitrile)ethane. In an aspect, the nitrile havingStructure N2 can be a bi(cyclohexylcarbonitrile), a substitutedbi(cyclohexylcarbonitrile), a bis(cyclohexylcarbonitrile)methane, asubstituted bis(cyclohexylcarbonitrile)methane, abis(cyclohexylcarbonitrile)ethane, or a substitutedbis(cyclohexylcarbonitrile)ethane; or alternatively, abi(cyclohexylcarbonitrile), a bis(cyclohexylcarbonitrile)methane, or abis(cyclohexylcarbonitrile)ethane. In an embodiment, the nitrile havingStructure N2 can be a bi(cyclohexylcarbonitrile) or a substitutedbi(cyclohexylcarbonitrile); alternatively, abis(cyclohexylcarbonitrile)methane or a substitutedbis(cyclohexylcarbonitrile)methane; or alternatively, abis(cyclohexylcarbonitrile)ethane or a substitutedbis(cyclohexylcarbonitrile)ethane. In some embodiments, the nitrilehaving Structure N2 can be a bi(cyclohexylcarbonitrile); alternatively,a substituted bi(cyclohexylcarbonitrile); alternatively, abis(cyclohexylcarbonitrile)methane; alternatively, a substitutedbis(cyclohexylcarbonitrile)methane; alternatively, abis(cyclohexylcarbonitrile)ethane; or alternatively, a substitutedbis(cyclohexylcarbonitrile)ethane. L² substituents and substituentpatterns for substituted L² bicyclylene groups, bis(cyclylene)methanegroups, and bis(cyclylene)ethane groups are generally disclosed hereinand can be utilized without limitation to further describe thesubstituted bi(cyclylcarbonitrile)s, substitutedbis(cyclylcarbonitrile)methanes, and substitutedbis(cyclylcarbonitrile)ethanes which can be utilized as the nitrilehaving Structure N2 in the various aspects and/or embodiments describedherein.

In an embodiment, the nitrile having Structure N2 can be4,4′-bicyclohexyldicarbonitrile,3,3′-disubstituted-4,4′-bicyclohexyldicarbonitrile, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyl-dicarbonitrile,bis(4-cyclohexylcarbonitrile)methane, abis(3-substituted-4-cyclohexylcarbonitrile)-methane, abis(3,5-disubstituted-4-cyclohexylcarbonitrile)methane,bis-1,2-(4-cyclohexylcarbonitrile)-ethane, abis-1,2-(3-substituted-4-cyclohexylcarbonitrile)ethane, abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonitrile)ethane. In someembodiments, the nitrile having Structure N2 can be4,4′-bicyclohexyldicarbonitrile, a3,3′-disubstituted-4,4′-bicyclohexyldicarbonitrile, a3,3′,5,5′-tetra-substituted-4,4′-bicyclohexyldicarbonitrile;alternatively, a bis(4-cyclohexylcarbonitrile)methane, abis(3-substituted-4-cyclohexylcarbonitrile)methane or abis(3,5-disubstituted-4-cyclohexylcarbonitrile)-methane; alternatively,bis-1,2-(4-cyclohexylcarbonitrile)ethane, abis-1,2-(3-substituted-4-cyclohexyl-carbonitrile)ethane or abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonitrile)ethane. In otherembodiments, the nitrile having Structure N2 can be4,4′-bicyclohexyldicarbonitrile; alternatively,3,3′-disubstituted-4,4′-bicyclohexyldicarbonitrile; alternatively, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyl-dicarbonitrile;alternatively, bis(4-cyclohexylcarbonitrile)methane; alternatively, abis(3-substituted-4-cyclohexylcarbonitrile)methane; alternatively, abis(3,5-disubstituted-4-cyclohexylcarbonitrile)methane; alternatively,bis-1,2-(4-cyclohexylcarbonitrile)ethane; alternatively, abis-1,2-(3-substituted-4-cyclohexylcarbonitrile)ethane; oralternatively, abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonitrile)-ethane. Generally,any bis(cyclohexylcarbonitrile)ethane disclosed herein (substituted orunsubstituted) can be a bis-1,1-(cyclohexylcarbonitrile)ethane or abis-1,2-(cyclohexylcarbonitrile)ethane group; alternatively, abis-1,1-(cyclohexylcarbonitrile)ethane; or alternatively, abis-1,2-(cyclohexyl-carbonitrile)ethane. Substituents for thesubstituted L² bicyclohex-4,4′-ylene groups,bis(cyclohex-4-ylene)methane groups, and abis-1,2-(cyclohex-4-ylene)ethane groups are generally disclosed hereinand can be utilized without limitation to further describe thesubstituted 4,4′-bicyclohexyldicarbonitriles, substitutedbis(4-cyclohexylcarbonitrile)methanes, and substitutedbis-1,2-(4-cyclohexylcarbonitrile)ethanes which can be utilized as thenitrile having Structure N2 in the various aspects and/or embodimentsdescribed herein.

In an aspect, the nitrile having Structure N2 can be abenzenedicarbonitrile or a substituted benzenedicarbonitrile. In anembodiment, the nitrile having Structure N2 can be abenzenedicarbonitrile; or alternatively, a substitutedbenzenedicarbonitrile. In some embodiments, the nitrile having StructureN2 can be 1,2-benzenedicarbonitrile or a substituted1,2-benzenedicarbonitrile; alternatively, 1,2-benzenedicarbonitrile; oralternatively, a substituted 1,2-benzenedicarbonitrile. In otherembodiments, the nitrile having Structure N2 can be1,3-benzenedicarbonitrile or a substituted 1,3-benzenedicarbonitrile;alternatively, 1,3-benzenedicarbonitrile; or alternatively, asubstituted 1,3-benzenedicarbonitrile. In yet other embodiments, thenitrile having Structure N2 can be 1,4-benzenedicarbonitrile or asubstituted 1,4-benzenedicarbonitrile; alternatively, a1,4-benzenedicarbonitrile; or alternatively, a substituted1,4-benzenedicarbonitrile. In further embodiments, the nitrile havingStructure N2 can be 1,2-benzenedicarbonitrile,1,3-benzenedicarbonitrile, or 1,4-benzenedicarbonitrile; alternatively,1,3-benzenedicarbonitrile, or 1,4-benzenedicarbonitrile. In otherembodiments, the nitrile having Structure N2 can be a substituted1,2-benzenedicarbonitrile, a substituted 1,3-benzenedicarbonitrile, or asubstituted 1,4-benzenedicarbonitrile; alternatively, a substituted1,3-benzenedicarbonitrile, or a substituted 1,4-benzenedicarbonitrile.In a non-limiting embodiment, the nitrile having Structure N2 can be a2,6-disubstituted 1,4-benzenedicarbonitrile, a 2,3-disubstituted1,4-benzenedicarbonitrile, a 2,5-disubstituted1,4-benzenedicarbonitrile, or a 2,3,5,6-tetrasubstituted1,4-benzenedicarbonitrile. In some embodiments, the nitrile havingStructure N2 can be a 2,6-disubstituted 1,4-benzenedicarbonitrile or a2,5-disubstituted 1,4-benzenedicarbonitrile; alternatively, a2,6-disubstituted 1,4-benzenedicarbonitrile; alternatively, a2,3-disubstituted 1,4-benzenedicarbonitrile; alternatively, a2,5-disubstituted 1,4-benzenedicarbonitrile; or alternatively, a2,3,5,6-tetrasubstituted 1,4-benzenedicarbonitrile. L² substituents andsubstituent patterns for substituted L² phenylene groups are generallydisclosed herein and can be utilized without limitation to furtherdescribe the substituted benzenedicarbonitriles which can be utilized asthe nitrile having Structure N2 in the various aspects and/orembodiments described herein.

In an aspect, the nitrile having Structure N2 can be anaphthalenedicarbonitrile or a substituted naphthalenedicarbonitrile. Inan embodiment, the nitrile having Structure N2 can be anaphthalene-dicarbonitrile; or alternatively, a substitutednaphthalenedicarbonitrile. In some embodiments, the nitrile havingStructure N2 can be 1,3-naphthalenedicarbonitrile, a substituted1,3-naphthalenedicarbonitrile, 1,4-naphthalenedicarbonitrile, asubstituted 1,4-naphthalenedicarbonitrile,1,5-naphthalenedicarbonitrile, a substituted1,5-naphthalenedicarbonitrile, 1,6-naphthalenedicarbonitrile, asubstituted 1,6-naphthalene-dicarbonitrile,1,7-naphthalenedicarbonitrile, a substituted1,7-naphthalenedicarbonitrile, 1,8-naphthalenedicarbonitrile, or asubstituted 1,8-naphthalenedicarbonitrile. In other embodiments, thenitrile having Structure N2 can be 1,3-naphthalenedicarbonitrile or asubstituted 1,3-naphthalene-dicarbonitrile; alternatively,1,4-naphthalenedicarbonitrile or a substituted1,4-naphthalenedicarbonitrile; alternatively,1,5-naphthalenedicarbonitrile or a substituted1,5-naphthalenedicarbonitrile; alternatively,1,6-naphthalenedicarbonitrile or a substituted1,6-naphthalenedicarbonitrile; alternatively,1,7-naphthalenedicarbonitrile or a substituted1,7-naphthalenedicarbonitrile; or alternatively,1,8-naphthalene-dicarbonitrile or a substituted1,8-naphthalenedicarbonitrile. In yet other embodiments, the nitrilehaving Structure N2 can be 1,3-naphthalenedicarbonitrile; alternatively,a substituted 1,3-naphthalene-dicarbonitrile; alternatively,1,4-naphthalenedicarbonitrile; alternatively, a substituted1,4-naphthalene-dicarbonitrile; alternatively,1,5-naphthalenedicarbonitrile; alternatively, a substituted1,5-naphthalene-dicarbonitrile; alternatively,1,6-naphthalenedicarbonitrile; alternatively, a substituted1,6-naphthalene-dicarbonitrile; alternatively,1,7-naphthalenedicarbonitrile; alternatively, a substituted1,7-naphthalene-dicarbonitrile; alternatively,1,8-naphthalenedicarbonitrile; or alternatively, a substituted1,8-naphthalene-dicarbonitrile. L² substituents and substituent patternsfor substituted L² naphthylene groups are generally disclosed herein andcan be utilized without limitation to further describe the substitutednaphthalene-dicarbonitriles which can be utilized as the nitrile havingStructure N2 in the various aspects and/or embodiments described herein.

In an aspect, the nitrile having Structure N2 can be abi(phenylcarbonitrile), a substituted bi(phenylcarbonitrile), abis(phenylcarbonitrile)methane group, a substitutedbis(phenylcarbonitrile)-methane group, a bis(phenylcarbonitrile)ethanegroup, or a substituted bis(phenylcarbonitrile)ethane group; oralternatively, a bi(phenylcarbonitrile), abis(phenylcarbonitrile)methane group, or abis(phenyl-carbonitrile)ethane group. In an embodiment, the nitrilehaving Structure N2 can be a bi(phenyl-carbonitrile) or a substitutedbi(phenylcarbonitrile); alternatively, bis(phenylcarbonitrile)methanegroup or a substituted bis(phenylcarbonitrile)methane group; oralternatively, a bis(phenylcarbonitrile)ethane group or a substitutedbis(phenylcarbonitrile)ethane group. In some embodiments, the nitrilehaving Structure N2 can be a bi(phenylcarbonitrile); alternatively, asubstituted bi(phenylcarbonitrile); alternatively, abis(phenylcarbonitrile)methane group; alternatively, a substitutedbis(phenylcarbonitrile)methane group; alternatively, abis(phenylcarbonitrile)ethane group; or alternatively, a substitutedbis(phenylcarbonitrile)ethane group.

In an embodiment, the nitrile having Structure N2 can be2,2′-bi(phenylcarbonitrile), a substituted 2,2′-bi(phenylcarbonitrile),3,3′-bi(phenylcarbonitrile), a substituted 3,3′-bi(phenyl-carbonitrile),4,4′-bi(phenylcarbonitrile), or a substituted4,4′-bi(phenylcarbonitrile); or alternatively,3,3′-bi(phenylcarbonitrile), a substituted 3,3′-bi(phenylcarbonitrile),4,4′-bi(phenylcarbonitrile), or a substituted4,4′-bi(phenylcarbonitrile). In some embodiments, the nitrile havingStructure N2 can be 2,2′-bi(phenylcarbonitrile) or a substituted2,2′-bi(phenylcarbonitrile); alternatively, 3,3′-bi(phenyl-carbonitrile)or a substituted 3,3′-bi(phenylcarbonitrile); or alternatively,4,4′-bi(phenylcarbonitrile) or a substituted4,4′-bi(phenylcarbonitrile). In other embodiments, the nitrile havingStructure N2 can be 2,2′-bi(phenylcarbonitrile); alternatively, asubstituted 2,2′-bi(phenylcarbonitrile); alternatively,3,3′-bi(phenylcarbonitrile); alternatively, a substituted3,3′-bi(phenylcarbonitrile); alternatively, 4,4′-bi(phenylcarbonitrile);or alternatively, a substituted 4,4′-bi(phenylcarbonitrile).

In an embodiment, the nitrile having Structure N2 can bebis(2-phenylcarbonitrile)methane, a substitutedbis(2-phenylcarbonitrile)methane, bis(3-phenylcarbonitrile)methane, asubstituted bis(3-phenylcarbonitrile)methane,bis(4-phenylcarbonitrile)methane, or a substitutedbis(4-phenylcarbonitrile)-methane; or alternatively,bis(3-phenylcarbonitrile)methane, a substitutedbis(3-phenylcarbonitrile)-methane, bis(4-phenylcarbonitrile)methane, ora substituted bis(4-phenylcarbonitrile)methane. In some embodiments, thenitrile having Structure N2 can be bis(2-phenylcarbonitrile)methane or asubstituted bis(2-phenylcarbonitrile)methane; alternatively,bis(3-phenylcarbonitrile)methane or a substitutedbis(3-phenylcarbonitrile)methane; or alternatively,bis(4-phenylcarbonitrile)methane or a substitutedbis(4-phenylcarbonitrile)methane. In other embodiments, the nitrilehaving Structure N2 can be bis(2-phenyl-carbonitrile)methane;alternatively, a substituted bis(2-phenylcarbonitrile)methane;alternatively, bis(3-phenylcarbonitrile)methane; alternatively, asubstituted bis(3-phenylcarbonitrile)methane; alternatively,bis(4-phenylcarbonitrile)methane; or alternatively, a substitutedbis(4-phenylcarbonitrile)methane.

In an embodiment, the nitrile having Structure N2 can bebis(2-phenylcarbonitrile)ethane, a substitutedbis(2-phenylcarbonitrile)ethane, bis(3-phenylcarbonitrile)ethane, asubstituted bis(3-phenyl-carbonitrile)ethane,bis(4-phenylcarbonitrile)ethane, or a substitutedbis(4-phenylcarbonitrile)ethane; or alternatively,bis(3-phenylcarbonitrile)ethane, a substitutedbis(3-phenylcarbonitrile)ethane, bis(4-phenyl-carbonitrile)ethane, or asubstituted bis(4-phenylcarbonitrile)ethane. In some embodiments, thenitrile having Structure N2 can be bis(2-phenylcarbonitrile)ethane or asubstituted bis(2-phenylcarbonitrile)-ethane; alternatively,bis(3-phenylcarbonitrile)ethane or a substitutedbis(3-phenylcarbonitrile)ethane; or alternatively,bis(4-phenylcarbonitrile)ethane or a substitutedbis(4-phenylcarbonitrile)ethane. In other embodiments, the nitrilehaving Structure N2 can be bis(2-phenylcarbonitrile)ethane;alternatively, a substituted bis(2-phenylcarbonitrile)ethane;alternatively, bis(3-phenylcarbonitrile)ethane; alternatively, asubstituted bis(3-phenylcarbonitrile)ethane; alternatively,bis(4-phenylcarbonitrile)ethane; or alternatively, a substitutedbis(4-phenylcarbonitrile)ethane. Generally, anybis(phenylcarbonitrile)ethane disclosed herein (substituted orunsubstituted) can be a bis-1,1-(phenylcarbonitrile)ethane or abis-1,2-(phenylcarbonitrile)ethane group; alternatively, abis-1,1-(phenylcarbonitrile)ethane; or alternatively, abis-1,2-(phenylcarbonitrile)ethane.

In an embodiment, the nitrile having Structure N2 can be a3,3′-disubstituted-4,4′-bi(phenyl-carbonitrile), a3,3′,5,5′-tetrasubstituted-4,4′-bi(phenylcarbonitrile), abis(3-substituted-4-phenyl-carbonitrile)methane, abis(3,5-disubstituted-4-phenylcarbonitrile)methane, abis-1,2-(3-substituted-4-phenylcarbonitrile)ethane, or abis-1,2-(3,5-disubstituted-4-phenylcarbonitrile)ethane. In someembodiments, the nitrile having Structure N2 can be a3,3′-disubstituted-4,4′-bi(phenylcarbonitrile) or a3,3′,5,5′-tetrasubstituted-4,4′-bi(phenylcarbonitrile); alternatively, abis(3-substituted-4-phenyl-carbonitrile)methane or abis(3,5-disubstituted-4-phenylcarbonitrile)methane; alternatively, abis-1,2-(3-substituted-4-phenylcarbonitrile)ethane or abis-1,2-(3,5-disubstituted-4-phenylcarbonitrile)ethane. In otherembodiments, the nitrile having Structure N2 can be a3,3′-disubstituted-4,4′-bi(phenylcarbonitrile); alternatively,3,3′,5,5′-tetrasubstituted-4,4′-bi(phenylcarbonitrile); alternatively, abis(3-substituted-4-phenylcarbonitrile)methane; alternatively, abis(3,5-disubstituted-4-phenylcarbonitrile)methane; alternatively, abis-1,2-(3-substituted-4-phenylcarbonitrile)ethane; or alternatively, abis-1,2-(3,5-disubstituted-4-phenylcarbonitrile)ethane.

L² substituents and substituent patterns for general and specificsubstituted L² biphenylene groups, bis(phenylene)methane groups, andbis(phenylene)ethane groups are generally disclosed herein and can beutilized without limitation to further describe the general and specificsubstituted bi(phenylcarbonitrile)s, substitutedbis(phenylcarbonitrile)methanes, and substitutedbis(phenylcarbonitrile)ethanes which can be utilized as the nitrilehaving Structure N2 in the various aspects and/or embodiments describedherein.

In an embodiment, the nitrile having Structure N2 can be adi(methylcarbonitrile)cycloalkane or a substituteddi(methylcarbonitrile)cycloalkane; alternatively, adi(methylcarbonitrile)cycloalkane. The cycloalkane group of thedi(methylcarbonitrile)cycloalkanes (substituted or unsubstituted) can becyclobutane group, a substituted cyclobutane group, a cyclopentanegroup, a substituted cyclopentane group, a cyclohexane group, asubstituted cyclohexane group, a cycloheptane group, a substitutedcycloheptane group, a cyclooctane group, or a substituted cyclooctanegroup; alternatively, a cyclopentane group, a substituted cyclopentanegroup, a cyclohexane group, or a substituted cyclohexane group;alternatively, a cyclobutane group or a substituted cyclobutane group;alternatively, a cyclopentane group or a substituted cyclopentane group;alternatively, a cyclohexane group or a substituted cyclohexane group;alternatively, a cycloheptane group or a substituted cycloheptane group;or alternatively, a cyclooctane group, or a substituted cyclooctanegroup. In some embodiments, the cycloalkane group of thedi(methylcarbonitrile)cycloalkanes (substituted or unsubstituted) can becyclobutane group, a cyclopentane group, a cyclohexane group, acycloheptane group, or a cyclooctane group; or alternatively, acyclopentane group or a cyclohexane group. In other embodiments, thecycloalkane group of the di(methylcarbonitrile)cycloalkanes (substitutedor unsubstituted) can be cyclopentane group; alternatively, asubstituted cyclopentane group; a cyclohexane group; or alternatively, asubstituted cyclohexane group.

In an embodiment, the nitrile having Structure N2 can be1,3-di(methylcarbonitrile)-cyclopentane, a substituted1,3-di(methylcarbonitrile)cyclopentane,1,3-di(methylcarbonitrile)-cyclohexane, a substituted1,3-di(methylcarbonitrile)cyclohexane,1,4-di(methylcarbonitrile)cyclohexane, or a substituted1,4-di(methylcarbonitrile)cyclohexane; alternatively,1,3-di(methylcarbonitrile)cyclo-pentane,1,3-di(methylcarbonitrile)cyclohexane, or1,4-di(methylcarbonitrile)cyclohexane. In some embodiments, the nitrilehaving Structure N2 can be 1,3-di(methylcarbonitrile)cyclopentane or asubstituted 1,3-di(methylcarbonitrile)cyclopentane; alternatively,1,3-di(methylcarbonitrile)cyclohexane or a substituted1,3-di(methylcarbonitrile)cyclohexane; alternatively,1,4-di(methylcarbonitrile)cyclo-hexane or a substituted1,4-di(methylcarbonitrile)cyclohexane; alternatively,1,3-di(methylcarbonitrile)-cyclohexane or a substituted1,3-di(methylcarbonitrile)cyclohexane; alternatively,1,4-di(methylcarbonitrile)cyclohexane or a substituted1,4-di(methylcarbonitrile)cyclohexane; alternatively,1,3-di(methyl-carbonitrile)cyclopentane; alternatively, a1,3-di(methylcarbonitrile)cyclohexane; or alternatively, a1,4-di(methylcarbonitrile)cyclohexane.

In an aspect, the nitrile having Structure N2 can be adi(methylcarbonitrile)benzene, or a substituteddi(methylcarbonitrile)benzene; alternatively, a di(methylcarbonitrile)benzene. In an embodiment, nitrile having Structure N2 can be a1,2-di(methylcarbonitrile)benzene, a substituted1,2-di(methylcarbonitrile)benzene, a 1,3-di(methylcarbonitrile)benzene,a substituted 1,3-di(methylcarbonitrile)benzene, a1,4-di(methylcarbonitrile)benzene, or a substituted1,4-di(methylcarbonitrile)benzene; alternatively, a1,2-di(methylcarbonitrile)benzene, a 1,3-di(methylcarbonitrile)benzene,or a 1,4-di(methylcarbonitrile)benzene. In some embodiments, nitrilehaving Structure N2 can be a 1,2-di(methylcarbonitrile)benzene or asubstituted 1,2-di(methylcarbonitrile)benzene; alternatively, a1,3-di(methylcarbonitrile)benzene or a substituted1,3-di(methylcarbonitrile)benzene; alternatively, a1,4-di(methylcarbonitrile)benzene or a substituted1,4-di(methylcarbonitrile)benzene; alternatively, a1,2-di(methylcarbonitrile)benzene; alternatively, a1,3-di(methylcarbonitrile)benzene; or alternatively, a1,4-di(methylcarbonitrile)benzene.

L² substituents for the general and specific substituteddi(methylene)cycloalkane groups and di(methylene)benzene groups aregenerally disclosed herein and can be utilized without limitation tofurther describe the general and specific substituteddi(methylcarbonitrile)cycloalkanes and substituteddi(methylcarbonitrile)benzenes which can be utilized as the nitrilehaving Structure N2 in the various aspects and/or embodiments describedherein.

In an aspect, the nitrile having Structure N2 can have Structure N6, N7,N8, N9, N10, N11, N12, N13, N14, N15, N16, N17, N18, or N19. In someembodiments, the nitrile having Structure N2 can have Structure N6, N7,or N8; alternatively, Structure N9, N10, N11, or N12; alternatively,Structure N13, N14, or N15; or alternatively, Structure N16, N17, N18,or N19. In other embodiments, the nitrile having Structure N2 can haveStructure N7 or N8; alternatively, Structure N9 or N10; alternatively,N11 or N12; alternatively, Structure N14 or N15; alternatively,Structure N16 or N17; or alternatively, Structure N18 or N19. In furtherembodiments, the nitrile having Structure N2 can have Structure N6;alternatively, Structure N7; alternatively, Structure N8; alternatively,Structure N9; alternatively, Structure N10; alternatively, StructureN11; alternatively, Structure N12; alternatively, Structure N13;alternatively, Structure N14; alternatively, Structure N15;alternatively, Structure N16; alternatively, Structure N17;alternatively, Structure N18 or alternatively, Structure N19.

TABLE 5 Dinitriles which can be utilized as the nitrile having StructureN2.

Structure N6

Structure N7

Structure N8

Structure N9

Structure N10

Structure N11

Structure N12

Structure N13

Structure N14

Structure N15

Structure N16

Structure N17

Structure N18

Structure N19

Aspects and embodiments for R^(1L)—R^(11L), R^(21L)—R^(31L),R^(21L′)—R^(31L′), R^(41L)—R^(51L), R^(41L′)—R^(51′), R^(62L)—R^(66L),R^(72L)—R^(76L), R^(72L′)—R^(76L′), R^(82L)—R^(86L), R^(82L′)—R^(86L′),and L^(a), are herein described for L2 which can be utilized inN2-phospinyl amidine compounds have Structure NP3, NP8, NP13, or NP18.These aspects and embodiments can be utilized without limitation todescribe the nitriles having Structures N6—N19 which can be utilized inthe various aspects and/or embodiments described herein.

In a non-limiting embodiment, the nitrile having Structure N2 can be1,4-benzenedicarbonitrile, 2,6-dimethyl-1,4-benzenedicarbonitrile,2,6-diethyl-1,4-benzenedicarbonitrile, 2,6-diisopropyl1,4-benzenedicarbonitrile, 2,6-di-tert-butyl-1,4-benzenedicarbonitrile,2,5-dimethyl-1,4-benzenedicarbonitrile,2,5-diethyl-1,4-benzenedicarbonitrile,2,5-diisopropyl-1,4-benzenedicarbonitrile,2,5-di-tert-butyl-1,4-benzenedicarbonitrile, or2,3,5,6-tetramethyl-1,4-benzenedicarbonitrile. In other non-limitingembodiments, the nitrile having Structure N2 can be1,4-benzenedicarbonitrile, 2,6-dimethyl-1,4-benzenedicarbonitrile,2,6-diethyl-1,4-benzenedicarbonitrile, 2,6-diisopropyl1,4-benzenedicarbonitrile, or2,6-di-tert-butyl-1,4-benzenedicarbonitrile; alternatively,2,5-dimethyl-1,4-benzenedicarbonitrile,2,5-diethyl-1,4-benzenedicarbonitrile,2,5-diisopropyl-1,4-benzenedicarbonitrile, or2,5-di-tert-butyl-1,4-benzenedicarbonitrile. In yet further non-limitingembodiments, the nitrile having Structure N2 can be1,4-benzenedicarbonitrile; alternatively,2,6-dimethyl-1,4-benzenedicarbonitrile; alternatively,2,6-diethyl-1,4-benzenedicarbonitrile; alternatively, 2,6-diisopropyl1,4-benzenedicarbonitrile; alternatively,2,6-di-tert-butyl-1,4-benzenedicarbonitrile; alternatively,2,5-dimethyl-1,4-benzene-dicarbonitrile; alternatively,2,5-diethyl-1,4-benzenedicarbonitrile; alternatively,2,5-diisopropyl-1,4-benzenedicarbonitrile; alternatively,2,5-di-tert-butyl-1,4-benzenedicarbonitrile; or alternatively,2,3,5,6-tetramethyl-1,4-benzenedicarbonitrile.

In a non-limiting embodiment, the nitrile having Structure N2 can be3,3′-dimethyl-4,4′-bi(phenylcarbonitrile),3,3′-diethyl-4,4′-bi(phenylcarbonitrile),3,3′-diisopropyl-4,4′-bi(phenyl-carbonitrile),3,3′-di-tert-butyl-4,4′-bi(phenylcarbonitrile),3,3′,5,5′-tetramethyl-4,4′-bi(phenyl-carbonitrile),3,3′,5,5′-tetraethyl-4,4′-bi(phenylcarbonitrile),3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonitrile), or3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenylcarbonitrile). In someembodiments, the nitrile having Structure N2 can be3,3′-dimethyl-4,4′-bi(phenylcarbonitrile),3,3′-diethyl-4,4′-bi(phenylcarbonitrile),3,3′-diisopropyl-4,4′-bi(phenylcarbonitrile), or3,3′-di-tert-butyl-4,4′-bi(phenylcarbonitrile); alternatively,3,3′,5,5′-tetramethyl-4,4′-bi(phenylcarbonitrile),3,3′,5,5′-tetraethyl-4,4′-bi(phenylcarbonitrile),3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonitrile), or3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenyl-carbonitrile). In otherembodiments, the nitrile having Structure N2 can be3,3′-dimethyl-4,4′-bi(phenyl-carbonitrile); alternatively,3,3′-diethyl-4,4′-bi(phenylcarbonitrile); alternatively,3,3′-diisopropyl-4,4′-bi(phenylcarbonitrile); alternatively,3,3′-di-tert-butyl-4,4′-bi(phenylcarbonitrile); alternatively,3,3′,5,5′-tetramethyl-4,4′-bi(phenylcarbonitrile); alternatively,3,3′,5,5′-tetraethyl-4,4′-bi(phenylcarbonitrile); alternatively,3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonitrile); or alternatively,3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenylcarbonitrile).

In a non-limiting embodiment, the nitrile having Structure N2 can bebis(3-methyl-4-phenylcarbonitrile)methane,bis(3-ethyl-4-phenylcarbonitrile)methane,bis(3-isopropyl-4-phenyl-carbonitrile)methane,bis(3-tert-butyl-4-phenylcarbonitrile)methanebis(3,5-dimethyl-4-phenylcarbonitrile)methane,bis(3,5-diethyl-4-phenylcarbonitrile)methane,bis(3,5-diisopropyl-4-phenylcarbonitrile)-methane, orbis(3,5-di-tert-butyl-4-phenylcarbonitrile)methane. In some embodiments,the nitrile having Structure N2 can bebis(3-methyl-4-phenylcarbonitrile)methane,bis(3-ethyl-4-phenylcarbonitrile)-methane,bis(3-isopropyl-4-phenylcarbonitrile)methane, orbis(3-tert-butyl-4-phenylcarbonitrile)methane; or alternatively,bis(3,5-dimethyl-4-phenylcarbonitrile)methane,bis(3,5-diethyl-4-phenylcarbonitrile)-methane,bis(3,5-diisopropyl-4-phenylcarbonitrile)methane, orbis(3,5-di-tert-butyl-4-phenylcarbonitrile)-methane. In otherembodiments, the nitrile having Structure N2 can bebis(3-methyl-4-phenylcarbonitrile)methane; alternatively,bis(3-ethyl-4-phenylcarbonitrile)methane; alternatively,bis(3-isopropyl-4-phenylcarbonitrile)methane; alternatively,bis(3-tert-butyl-4-phenylcarbonitrile)methane; alternatively,bis(3,5-dimethyl-4-phenylcarbonitrile)methane; alternatively,bis(3,5-diethyl-4-phenylcarbonitrile)-methane; alternatively,bis(3,5-diisopropyl-4-phenylcarbonitrile)methane; or alternatively,bis(3,5-di-tert-butyl-4-phenylcarbonitrile)methane.

In a non-limiting embodiment, the nitrile having Structure N2 can bebis(3-methyl-4-phenyl-carbonitrile)ethane,bis(3-ethyl-4-phenylcarbonitrile)ethane,bis(3-isopropyl-4-phenylcarbonitrile)ethane,bis(3-tert-butyl-4-phenylcarbonitrile)ethane,bis(3,5-dimethyl-4-phenylcarbonitrile)ethane,bis(3,5-diethyl-4-phenylcarbonitrile)ethane,bis(3,5-diisopropyl-4-phenylcarbonitrile)ethane, orbis(3,5-di-tert-butyl-4-phenylcarbonitrile)ethane. In some embodiments,the nitrile having Structure N2 can bebis(3-methyl-4-phenylcarbonitrile)ethane,bis(3-ethyl-4-phenylcarbonitrile)ethane,bis(3-isopropyl-4-phenyl-carbonitrile)ethane, orbis(3-tert-butyl-4-phenylcarbonitrile)ethane; alternatively,bis(3,5-dimethyl-4-phenylcarbonitrile)ethane,bis(3,5-diethyl-4-phenylcarbonitrile)ethane,bis(3,5-diisopropyl-4-phenyl-carbonitrile)ethane, orbis(3,5-di-tert-butyl-4-phenylcarbonitrile)ethane. In other embodiments,the nitrile having Structure N2 can bebis(3-methyl-4-phenylcarbonitrile)ethane; alternatively,bis(3-ethyl-4-phenyl-carbonitrile)ethane; alternatively,bis(3-isopropyl-4-phenylcarbonitrile)ethane; alternatively,bis(3-tert-butyl-4-phenylcarbonitrile)ethane; alternatively,bis(3,5-dimethyl-4-phenylcarbonitrile)ethane; alternatively,bis(3,5-diethyl-4-phenylcarbonitrile)ethane; alternatively,bis(3,5-diisopropyl-4-phenyl-carbonitrile)ethane; or alternatively,bis(3,5-di-tert-butyl-4-phenylcarbonitrile)ethane. Generally, thesesubstituted bis(phenylcarbonitrile)ethanes can bebis-1,1-(phenylcarbonitrile)ethane orbis-1,2-(phenyl-carbonitrile)ethane group; alternatively,bis-1,1-(phenylcarbonitrile)ethane; or alternatively,bis-1,2-(phenylcarbonitrile)ethane.

In an aspect, D² of the nitrile having Structure N3 can be any D²described herein. D² is described herein as a feature of theN²-phosphinyl amidine metal salt complexes having Structure NP5, NP10,NP15, or NP20 utilized in various aspects of this disclosure. Since thenitriles having Structure N3 can be utilized to prepare embodiments ofthe N²-phospinyl amidine compounds having Structure NP5, NP10, NP15, orNP20, the aspects and embodiments of D² can utilized without limitationto further describe the nitriles having Structure N3.

Within this disclosure, acid halides can be used to ultimately preparethe N²-phosphinyl amidine compounds and/or the N²-phosphinyl amidinemetal salt complexes utilized in various aspects of this disclosure. Invarious embodiments, acid halides which can be utilized can haveStructure AC1, AC2, or AC3; alternatively, AC1; alternatively, AC2; oralternatively, AC3. R², L², and D² are described as

R², L², D², and q within acid halide Structures A1-A3 are independentlydescribed as features of the N²-phospinyl amidine compounds havingStructures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20. Sincethe acid halide having Structures A1-A3 are ultimately utilized toprepare embodiments of N²-phospinyl amidine compounds having StructuresNP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20, the R², L², D², andq descriptions for the N²-phospinyl amidine compounds can be utilizedwithout limitation to further describe the acid halide Structures A1-A3.Additionally, X³ has been described within the methods of preparingN²-phospinyl amidine compounds having Structures NP1—NP10, NP11, NP13,NP15, NP16, NP18, and/or NP20 and this description can be utilizedwithout limitation to further describe the acid halide Structures A1-A3.

In an aspect, the acid halide having Structure AC1 can be an acetylhalide, a propionyl halide, a butanoyl halide, a pentanoyl halide, ahexanoyl halide, a heptanoyl halide, an octanoyl halide, a nonanoylhalide, a decanoyl halide, an undecanoyl halide, a dodecanoyl halide, atridecanoyl halide, a tetradecanoyl halide, a pentadecanoyl halide, ahexadecanoyl halide, a heptadecanoyl halide, an octadecanoyl halide, anonadecanoyl halide, or an eicosanoyl halide; or alternatively, anacetyl halide, a propionyl halide, a butanoyl halide, a pentanoylhalide, a hexanoyl halide, a heptanoyl halide, an octanoyl halide, anonanoyl halide, a decanoyl halide, or an undecanoyl halide. In someembodiments, the acid halide having Structure AC1 can be an acetylhalide, a propionyl halide, an n-butanoyl halide, a 2-methylpropanylhalide, an n-pentanoyl halide, a 3-methylbutanoyl halide, a2-methylbutanol halide, a 2,2-dimethylpropanoyl halide, an n-hexanoylhalide, a 3-methylbutanoyl halide, a 2-methylbutanoyl halide, or a3,3-dimethylbutanoyl halide; alternatively, an acetyl halide, apropanoyl halide, a 2-methylpropanoyl halide, a 2,2-dimethylpropanonylhalide, or a 3,3-dimethylbutanoyl halide; alternatively, an acetylhalide; alternatively, a propanoyl halide; alternatively, an n-butanoylhalide; alternatively, an n-pentanoyl halide; alternatively, a2-methylpropanonyl halide; alternatively, a 2,2-dimethyl propanonylhalide; or alternatively, a 3,3-dimethylbutanoyl halide.

In an aspect, the acid halide having Structure AC1 can be acetylchloride, propionyl chloride, a butanoyl chloride, a pentanoyl chloride,a hexanoyl chloride, a heptanoyl chloride, an octanoyl chloride, anonanoyl chloride, a decanoyl chloride, an undecanoyl chloride, adodecanoyl chloride, a tridecanoyl chloride, a tetradecanoyl chloride, apentadecanoyl chloride, a hexadecanoyl chloride, a heptadecanoyl, anoctadecanoyl chloride, a nonadecanoyl chloride, or an eicosanoylchloride; or alternatively, acetyl chloride, propionyl chloride, abutanoyl chloride, a pentanoyl chloride, a hexanoyl chloride, aheptanoyl chloride, an octanoyl chloride, a nonanoyl chloride, adecanoyl chloride, or an undecanoyl chloride. In some embodiments, theacid halide having Structure AC1 can be acetyl chloride, propionylchloride, n-butanoyl chloride, 2-methylpropanyl chloride, n-pentanoylchloride, 3-methylbutanoyl chloride, 2-methylbutanol chloride,2,2-dimethylpropanoyl chloride, n-hexanoyl chloride, 3-methylbutanoylchloride, 2-methylbutanoyl chloride group, or 3,3-dimethylbutanoylchloride; alternatively, acetyl chloride, propanoyl chloride,2-methylpropanoyl chloride, 2,2-dimethylpropanonyl chloride, or3,3-dimethylbutanoyl chloride; alternatively, acetyl chloride;alternatively, propanoyl chloride; alternatively, n-butanoyl chloride;alternatively, n-pentanoyl chloride; alternatively, 2-methylpropanonylchloride; alternatively, 2,2-dimethyl propanonyl chloride; oralternatively, 3,3-dimethylbutanoyl chloride.

In an aspect, the acid halide having Structure AC1 can be acyclobutylcarbonyl halide, a substituted cyclobutylcarbonyl halide, acyclopentylcarbonyl halide, a substituted cyclopentylcarbonyl halide, acyclohexylcarbonyl halide, a substituted cyclohexylcarbonyl halide, acycloheptylcarbonyl halide, a substituted cycloheptylcarbonyl halide, acyclooctylcarbonyl halide, or a substituted cyclooctylcarbonyl halide.In some embodiments, the acid halide can be a cyclopentylcarbonylhalide, a substituted cyclopentylcarbonyl halide, a cyclohexylcarbonylhalide, a substituted cyclohexylcarbonyl halide. In other embodiments,the acid halide can be a cyclobutylcarbonyl halide or a substitutedcyclobutylcarbonyl halide; alternatively, a cyclopentylcarbonyl halideor a substituted cyclopentyl-carbonyl halide; alternatively, acyclohexylcarbonyl halide or a substituted cyclohexylcarbonyl halide;alternatively, a cycloheptylcarbonyl halide or a substitutedcycloheptylcarbonyl halide; or alternatively, a cyclooctylcarbonylhalide, or a substituted cyclooctylcarbonyl halide. In furtherembodiments, the acid halide can be a cyclopentylcarbonyl halide;alternatively, a substituted cyclopentylcarbonyl halide; alternatively,a cyclohexylcarbonyl halide; or alternatively, a substitutedcyclohexylcarbonyl halide. In other embodiments, the acid halide havingStructure AC1 can be cyclobutylcarbonyl chloride, a substitutedcyclobutylcarbonyl chloride, cyclopentylcarbonyl chloride, a substitutedcyclopentylcarbonyl chloride, cyclohexylcarbonyl chloride, a substitutedcyclohexylcarbonyl chloride, cycloheptylcarbonyl chloride, a substitutedcycloheptylcarbonyl chloride, cyclooctylcarbonyl chloride, or asubstituted cyclooctylcarbonyl chloride. In some other embodiments, theacid halide can be cyclopentylcarbonyl chloride, a substitutedcyclopentylcarbonyl chloride, cyclohexylcarbonyl chloride, or asubstituted cyclohexylcarbonyl chloride. In further embodiments, theacid chloride can be cyclobutylcarbonyl chloride or a substitutedcyclobutylcarbonyl chloride; alternatively, cyclopentylcarbonyl chlorideor a substituted cyclopentylcarbonyl chloride; alternatively,cyclohexylcarbonyl chloride or a substituted cyclohexylcarbonylchloride; alternatively, cycloheptylcarbonyl chloride or a substitutedcycloheptyl-carbonyl chloride; or alternatively, cyclooctylcarbonylchloride, or a substituted cyclooctylcarbonyl chloride. In yet furtherembodiments, the acid chloride can be cyclopentylcarbonyl chloride;alternatively, a substituted cyclopentylcarbonyl chloride;cyclohexylcarbonyl chloride; or alternatively, a substitutedcyclohexylcarbonyl chloride. Substituents and substituents patterns forthe R² cycloalkyl groups are described herein and can be utilizedwithout limitation to further describe the substitutedcycloalkylcarbonyl halides or cycloalkylcarbonyl chlorides which can beutilized in aspects and/or embodiments described herein.

In an aspect, the acid having Structure AC1 can have Structure AC4. TheR^(21c), R^(22c), R^(23c), R^(24c), and R^(25c) substituents,substituent patterns, and n for the R² group having Structure G3 aredescribed

herein and can be utilized without limitation to describe the acidhalide having Structure AC4 which can be utilized in the various aspectsand/or embodiments described herein. In an embodiment, the X³ of theacid halide having Structure AC4 can be a chloride or a bromide;alternatively, a chloride; or alternatively, a bromide.

In an embodiment, the acid halide having Structure AC1 can be benzoylhalide or a substituted benzoyl halide. In some embodiments, the acidhalide having Structure AC1 can be benzoyl halide; or alternatively, asubstituted benzoyl halide. In an embodiment, the substituted benzoylhalide can be a 2-substituted benzoyl halide, a 3-substituted benzoylhalide, a 4-substituted benzoyl halide, a 2,4-disubstituted benzoylhalide, a 2,6-disubstituted benzoyl halide, a 3,5-disubstituted benzoylhalide, or a 2,4,6-trisubstituted benzoyl halide. In other embodiments,the substituted benzoyl halide can be a 2-substituted benzoyl halide, a4-substituted benzoyl halide, a 2,4-disubstituted benzoyl halide, or a2,6-disubstituted benzoyl halide; alternatively, a 3-substituted benzoylhalide or a 3,5-disubstituted benzoyl halide; alternatively, a2-substituted benzoyl halide or a 4-substituted benzoyl halide;alternatively, a 2,4-disubstituted benzoyl halide or a 2,6-disubstitutedbenzoyl halide; alternatively, a 2-substituted benzoyl halide;alternatively, a 3-substituted benzoyl halide; alternatively, a4-substituted benzoyl halide; alternatively, a 2,4-disubstituted benzoylhalide; alternatively, a 2,6-disubstituted benzoyl halide;alternatively, 3,5-disubstituted benzoyl halide; or alternatively, a2,4,6-trisubstituted benzoyl halide. In other embodiments, the acidhalide having Structure AC1 can be benzoyl chloride or a substitutedbenzoyl chloride. In some other embodiments, the acid halide havingStructure AC1 can be benzoyl chloride; or alternatively, a substitutedbenzoyl chloride. In further embodiments, the substituted benzoylchloride can be a 2-substituted benzoyl chloride, a 3-substitutedbenzoyl chloride, a 4-substituted benzoyl chloride, a 2,4-disubstitutedbenzoyl chloride, a 2,6-disubstituted benzoyl chloride, a3,5-disubstituted benzoyl chloride, or a 2,4,6-trisubstituted benzoylchloride. In yet further embodiments, the substituted benzoyl chloridecan be a 2-substituted benzoyl chloride, a 4-substituted benzoylchloride, a 2,4-disubstituted benzoyl chloride, or a 2,6-disubstitutedbenzoyl chloride; alternatively, a 3-substituted benzoyl chloride or a3,5-disubstituted benzoyl chloride; alternatively, a 2-substitutedbenzoyl chloride or a 4-substituted benzoyl chloride; alternatively, a2,4-disubstituted benzoyl chloride or a 2,6-disubstituted benzoylchloride; alternatively, a 2-substituted benzoyl chloride;alternatively, a 3-substituted benzoyl chloride; alternatively, a4-substituted benzoyl chloride; alternatively, a 2,4-disubstitutedbenzoyl chloride; alternatively, a 2,6-disubstituted benzoyl chloride;alternatively, a 3,5-disubstituted benzoyl chloride; or alternatively, a2,4,6-trisubstituted benzoyl chloride. Substituents for the R² phenylgroups are generally disclosed herein and can be utilized withoutlimitation to further describe the substituted benzoyl halides orbenzoyl chlorides which can be utilized in the various aspects and/orembodiments described herein.

In an aspect, the acid halide having Structure AC1 can have StructureAC5. The R²², R²³, R²⁴, R²⁵, and R²⁶ substituents and substituentpatterns for the R² group having Structure G4 are described

herein and can be utilized without limitation to describe the acidhalide having Structure AC5 which can be utilized in the various aspectsand/or embodiments described herein. In an embodiment, the X³ of theacid halide having Structure AC5 can be a chloride or a bromide;alternatively, a chloride; or alternatively, a bromide.

In an aspect, the acid halide having Structure AC1 can be apyridinecarbonyl halide, a substituted pyridinecarbonyl halide, afurancarbonyl halide, a substituted furancarbonyl halide, athiophenecarbonyl halide, or a substituted thiophenecarbonyl halide. Inan embodiment, the acid halide having Structure AC1 can be apyridinecarbonyl halide or a substituted pyridinecarbonyl halide;alternatively, a furancarbonyl halide or a substituted furancarbonylhalide; or alternatively, a thiophene-carbonyl halide, or a substitutedthiophenecarbonyl halide. In some embodiments, the acid halide havingStructure AC1 can be a pyridinecarbonyl halide, a furancarbonyl halide,or a thiophenecarbonyl halide. In other embodiments, the acid halidehaving Structure AC1 can be a pyridinecarbonyl halide; alternatively, asubstituted pyridinecarbonyl halide; alternatively, a furancarbonylhalide; alternatively, a substituted furancarbonyl halide;alternatively, a thiophenecarbonyl halide; or alternatively, asubstituted thiophenecarbonyl halide. In other embodiments, the acidhalide having Structure AC1 can be a pyridine-carbonyl chloride, asubstituted pyridinecarbonyl chloride, a furancarbonyl chloride, asubstituted furancarbonyl chloride, a thiophenecarbonyl chloride, or asubstituted thiophenecarbonyl chloride. In some other embodiments, theacid halide having Structure AC1 can be a pyridinecarbonyl chloride or asubstituted pyridinecarbonyl chloride; alternatively, a furancarbonylchloride or a substituted furan-carbonyl chloride; or alternatively, athiophenecarbonyl chloride, or a substituted thiophenecarbonyl chloride.In yet other embodiments, the acid halide having Structure AC1 can be apyridinecarbonyl chloride, a furancarbonyl chloride, or athiophenecarbonyl chloride. In further embodiments, the acid halidehaving Structure AC1 can be a pyridinecarbonyl chloride; alternatively,a substituted pyridine-carbonyl chloride; alternatively, a furancarbonylchloride; alternatively, a substituted furancarbonyl chloride;alternatively, a thiophenecarbonyl chloride; or alternatively, asubstituted thiophenecarbonyl chloride.

In an embodiment, the pyridinecarbonyl halide (or substitutedpyridinecarbonyl halide) can be 2-pyridinecarbonyl halide, a substituted2-pyridinecarbonyl halide, a 3-pyridinecarbonyl halide, a substituted3-pyridinecarbonyl halide, a 4-pyridinecarbonyl halide, or a substituted4-pyridinecarbonyl halide; alternatively, 2-pyridinecarbonyl halide,3-pyridinecarbonyl halide, or 4-pyridinecarbonyl halide. In someembodiments, the pyridinecarbonyl halide (or substitutedpyridinecarbonyl halide) can be a 2-pyridinecarbonyl halide or asubstituted 2-pyridinecarbonyl halide; alternatively, a3-pyridinecarbonyl halide or a substituted 3-pyridinecarbonyl halide;alternatively, a 4-pyridinecarbonyl halide, or a substituted4-pyridinecarbonyl halide; alternatively, a 2-pyridinecarbonyl halide;alternatively, a substituted 2-pyridinecarbonyl halide; alternatively, a3-pyridinecarbonyl halide; alternatively, a substituted3-pyridinecarbonyl halide; alternatively, a 4-pyridinecarbonyl halide;or alternatively, a substituted 4-pyridinecarbonyl halide. In anembodiment, the pyridinecarbonyl halide (or substituted pyridinecarbonylhalide) can be a 2-substituted-3-pyridinecarbonyl halide, a4-substituted-3-pyridine-carbonyl halide, a5-substituted-3-pyridinecarbonyl halide, a6-substituted-3-pyridinecarbonyl halide, a2,4-disubstituted-3-pyridinecarbonyl halide, a2,6-disubstituted-3-pyridinecarbonyl halide, or a2,4,6-trisubstituted-3-pyridinecarbonyl halide; alternatively, a2-substituted-3-pyridinecarbonyl halide, a4-substituted-3-pyridinecarbonyl halide, a6-substituted-3-pyridinecarbonyl halide; alternatively, a2,4-disubstituted-3-pyridinecarbonyl halide or a2,6-disubstituted-3-pyridinecarbonyl halide; alternatively, a2-substituted-3-pyridinecarbonyl halide; alternatively, a4-substituted-3-pyridinecarbonyl halide; alternatively, a5-substituted-3-pyridinecarbonyl halide; alternatively, a6-substituted-3-pyridinecarbonyl halide; alternatively, a2,4-disubstituted-3-pyridinecarbonyl halide; alternatively, a2,6-disubstituted-3-pyridinecarbonyl halide; or alternatively, a2,4,6-trisubstituted-3-pyridinecarbonyl halide. In an embodiment, thepyridinecarbonyl halide (or substituted-pyridinecarbonyl halide) can bea 2-substituted-4-pyridinecarbonyl halide, a3-substituted-4-pyridinecarbonyl halide, a5-substituted-4-pyridinecarbonyl halide, a6-substituted-4-pyridinecarbonyl halide, a2,6-disubstituted-4-pyridinecarbonyl halide, or a3,5-disubstituted-4-pyridinecarbonyl halide; alternatively, a2-substituted-4-pyridinecarbonyl halide, or a6-substituted-4-pyridinecarbonyl halide; alternatively, a3-substituted-4-pyridinecarbonyl halide or a5-substituted-4-pyridinecarbonyl halide; alternatively, a2-substituted-4-pyridinecarbonyl halide; alternatively, a3-substituted-4-pyridinecarbonyl halide; alternatively, a5-substituted-4-pyridinecarbonyl halide; alternatively, a6-substituted-4-pyridinecarbonyl halide; alternatively, a2,6-disubstituted-4-pyridinecarbonyl halide; or alternatively, a3,5-disubstituted-4-pyridinecarbonyl halide. In other embodiments, thepyridinecarbonyl chloride (or substituted pyridinecarbonyl chloride) canbe 2-pyridine-carbonyl chloride, a substituted 2-pyridinecarbonylchloride, 3-pyridinecarbonyl chloride, a substituted 3-pyridinecarbonylchloride, 4-pyridinecarbonyl chloride, or a substituted4-pyridinecarbonyl chloride; or alternatively, 2-pyridinecarbonylchloride, 3-pyridinecarbonyl chloride, or 4-pyridinecarbonyl chloride.In some embodiments, the pyridinecarbonyl chloride (or substitutedpyridinecarbonyl chloride) can be 2-pyridinecarbonyl chloride or asubstituted 2-pyridinecarbonyl chloride; alternatively,3-pyridine-carbonyl chloride or a substituted 3-pyridinecarbonylchloride; alternatively, 4-pyridinecarbonyl chloride, or a substituted4-pyridinecarbonyl chloride; alternatively, 2-pyridinecarbonyl chloride;alternatively, a substituted 2-pyridinecarbonyl chloride; alternatively,3-pyridinecarbonyl chloride; alternatively, a substituted3-pyridinecarbonyl chloride; alternatively, 4-pyridinecarbonyl chloride;or alternatively, a substituted 4-pyridinecarbonyl chloride. In someother embodiments, the pyridinecarbonyl chloride (or substitutedpyridinecarbonyl chloride) can be a 2-substituted-3-pyridinecarbonylchloride, a 4-substituted-3-pyridinecarbonyl chloride, a5-substituted-3-pyridinecarbonyl chloride, a6-substituted-3-pyridine-carbonyl chloride, a2,4-disubstituted-3-pyridinecarbonyl chloride, a2,6-disubstituted-3-pyridinecarbonyl chloride, or a2,4,6-trisubstituted-3-pyridinecarbonyl chloride; alternatively, a2-substituted-3-pyridine-carbonyl chloride, a4-substituted-3-pyridinecarbonyl chloride, or a6-substituted-3-pyridinecarbonyl chloride; alternatively, a2,4-disubstituted-3-pyridinecarbonyl chloride or a2,6-disubstituted-3-pyridine-carbonyl chloride; alternatively, a2-substituted-3-pyridinecarbonyl chloride; alternatively, a4-substituted-3-pyridinecarbonyl chloride; alternatively, a5-substituted-3-pyridinecarbonyl chloride; alternatively, a6-substituted-3-pyridinecarbonyl chloride; alternatively, a2,4-disubstituted-3-pyridine-carbonyl chloride; alternatively, a2,6-disubstituted-3-pyridinecarbonyl chloride; or alternatively, a2,4,6-trisubstituted-3-pyridinecarbonyl chloride. In yet otherembodiments, the pyridinecarbonyl chloride (orsubstituted-pyridinecarbonyl chloride) can be a2-substituted-4-pyridinecarbonyl chloride, a3-substituted-4-pyridinecarbonyl chloride, a5-substituted-4-pyridinecarbonyl chloride, a6-substituted-4-pyridine-carbonyl chloride, a2,6-disubstituted-4-pyridinecarbonyl chloride, or a3,5-disubstituted-4-pyridine-carbonyl chloride; alternatively, a2-substituted-4-pyridinecarbonyl chloride or a6-substituted-4-pyridine-carbonyl chloride; alternatively, a3-substituted-4-pyridinecarbonyl chloride or a5-substituted-4-pyridine-carbonyl chloride; alternatively, a2-substituted-4-pyridinecarbonyl chloride; alternatively, a3-substituted-4-pyridinecarbonyl chloride; alternatively, a5-substituted-4-pyridinecarbonyl chloride; alternatively, a6-substituted-4-pyridinecarbonyl chloride; alternatively, a2,6-disubstituted-4-pyridine-carbonyl chloride; or alternatively, a3,5-disubstituted-4-pyridinecarbonyl chloride. Substituents for the R²pyridinyl groups are generally disclosed herein and can be utilizedwithout limitation to further describe the substituted pyridinecarbonylhalides or substituted pyridinecarbonyl chlorides which can be utilizedin the various aspects and/or embodiments described herein.

In an embodiment, the furancarbonyl halide (or substituted furancarbonylhalide) can be a 2-furancarbonyl halide, a substituted 2-furancarbonylhalide, a 3-furancarbonyl halide, or a substituted 3-furancarbonylhalide; alternatively, a 2-furancarbonyl halide or a 3-furancarbonylhalide. In some embodiments, the furancarbonyl halide (or substitutedfurancarbonyl halide) can be a 2-furancarbonyl halide or a substituted2-furancarbonyl halide; alternatively, a 3-furancarbonyl halide or asubstituted 3-furancarbonyl halide; alternatively, 2-furancarbonylhalide; alternatively, a substituted 2-furancarbonyl halide;alternatively, a 3-furancarbonyl halide; or alternatively, a substituted3-furancarbonyl halide. In an embodiment, the furancarbonyl halide (orsubstituted furancarbonyl halide) can be a 2-substituted-3-furancarbonylhalide, a 4-substituted-3-furancarbonyl halide, or a2,4-disubstituted-3-furancarbonyl halide; alternatively, a2-substituted-3-furancarbonyl halide; alternatively, a4-substituted-3-furancarbonyl halide; or alternatively, a2,4-disubstituted-3-furancarbonyl halide. In other embodiments, thefurancarbonyl chloride (or substituted furancarbonyl chloride) can be2-furancarbonyl chloride, a substituted 2-furancarbonyl chloride,3-furancarbonyl chloride, or a substituted 3-furancarbonyl chloride;alternatively, 2-furancarbonyl chloride or 3-furancarbonyl chloride. Insome other embodiments, the furancarbonyl chloride (or substitutedfurancarbonyl chloride) can be a 2-furancarbonyl chloride or asubstituted 2-furancarbonyl chloride; alternatively, 3-furancarbonylchloride or a substituted 3-furancarbonyl chloride; alternatively,2-furancarbonyl chloride; alternatively, a substituted 2-furan-carbonylchloride; alternatively, 3-furancarbonyl chloride; or alternatively, asubstituted 3-furancarbonyl chloride. In yet other embodiments, thefurancarbonyl chloride (or substituted furancarbonyl chloride) can be a2-substituted-3-furancarbonyl chloride, a 4-substituted-3-furancarbonylchloride, or a 2,4-disubstituted-3-furancarbonyl chloride;alternatively, a 2-substituted-3-furancarbonyl chloride; alternatively,a 4-substituted-3-furancarbonyl chloride; or alternatively, a2,4-disubstituted-3-furan-carbonyl chloride. Substituents for the R²furyl groups are generally disclosed herein and can be utilized withoutlimitation to further describe the substituted furancarbonyl halides orsubstituted furancarbonyl chlorides which can be utilized in the variousaspects and/or embodiments described herein.

In an embodiment, the thiophenecarbonyl halide (or substitutedthiophenecarbonyl halide) can be a 2-thiophenecarbonyl halide, asubstituted 2-thiophenecarbonyl halide, a 3-thiophenecarbonyl halide, ora substituted 3-thiophenecarbonyl halide; alternatively, a2-thiophenecarbonyl halide or a 3-thiophenecarbonyl halide. In someembodiments, the thiophenecarbonyl halide (or substitutedthiophenecarbonyl halide) group can be a 2-thiophenecarbonyl halide or asubstituted 2-thiophene-carbonyl halide; alternatively, a3-thiophenecarbonyl halide or a substituted 3-thiophenecarbonyl halide;alternatively, a 2-thiophenecarbonyl halide; alternatively, asubstituted 2-thiophenecarbonyl halide; alternatively, a3-thiophenecarbonyl halide; or alternatively, a substituted3-thiophenecarbonyl halide. In an embodiment, the thiophenecarbonylhalide (or substituted thiophenecarbonyl halide) can be a2-substituted-3-thiophenecarbonyl halide, a4-substituted-3-thiophenecarbonyl halide, or a2,4-disubstituted-3-thiophenecarbonyl halide; alternatively, a2-substituted-3-thiophenecarbonyl halide; alternatively, a4-substituted-3-thiophenecarbonyl halide; or alternatively, a2,4-disubstituted-3-thiophenecarbonyl halide. In other embodiments, thethiophenecarbonyl chloride (or substituted thiophenecarbonyl chloride)can be 2-thiophenecarbonyl chloride, a substituted 2-thiophenecarbonylchloride, 3-thiophenecarbonyl chloride, or a substituted3-thiophenecarbonyl chloride; alternatively, 2-thiophenecarbonylchloride or 3-thiophenecarbonyl chloride. In some other embodiments, thethiophenecarbonyl chloride (or substituted thiophenecarbonyl chloride)group can be 2-thiophenecarbonyl chloride or a substituted2-thiophenecarbonyl chloride; alternatively, 3-thiophenecarbonylchloride or a substituted 3-thiophenecarbonyl chloride; alternatively,2-thiophenecarbonyl chloride; alternatively, a substituted2-thiophenecarbonyl chloride; alternatively, 3-thiophenecarbonylchloride; or alternatively, a substituted 3-thiophenecarbonyl chloride.In further embodiments, the thiophenecarbonyl chloride (or substitutedthiophenecarbonyl chloride) can be a 2-substituted-3-thiophenecarbonylchloride, a 4-substituted-3-thiophenecarbonyl chloride, or a2,4-disubstituted-3-thiophenecarbonyl chloride; alternatively, a2-substituted-3-thiophenecarbonyl chloride; alternatively, a4-substituted-3-thiophene-carbonyl chloride; or alternatively, a2,4-disubstituted-3-thiophenecarbonyl chloride. Substituents for the R²thienyl groups are generally disclosed herein and can be utilizedwithout limitation to further describe the substituted thiophenecarbonylhalides or substituted thiophenecarbonyl chlorides which can be utilizedin the various aspects and/or embodiments described herein.

In a non-limiting embodiment, the acid halide having Structure AC1 canbe a benzoyl halide, a 2-alkylbenzoyl halide, a 3-alkylbenzoyl halide, a4-alkylbenzoyl halide, a 2,4-dialkylbenzoyl halide a 2,6-dialkylbenzoylhalide, a 3,5-dialkylbenzoyl halide, or a 2,4,6-trialkylbenzoyl halide;alternatively, a 2-alkylbenzoyl halide, a 4-alkylbenzoyl halide, a2,4-dialkylbenzoyl halide, a 2,6-dialkylbenzoyl halide, or a2,4,6-trialkylbenzoyl halide; alternatively, a 2-alkylbenzoyl halide ora 4-alkylbenzoyl halide; alternatively, a 2,4-dialkylbenzoyl halide a2,6-dialkylbenzoyl halide; alternatively, a 3-alkylbenzoyl halide or a3,5-dialkylbenzoyl halide; alternatively, a 2-alkylbenzoyl halide or a2,6-dialkylbenzoyl halide; alternatively, a benzoyl halide;alternatively, a 2-alkylbenzoyl halide; alternatively, a 3-alkyl-benzoylhalide; alternatively, a 4-alkylbenzoyl halide; alternatively, a2,4-dialkylbenzoyl halide; alternatively, a 2,6-dialkylbenzoyl halide;alternatively, a 3,5-dialkylbenzoyl halide; or alternatively, a2,4,6-trialkylbenzoyl halide. In another non-limiting embodiment, theacid halide having Structure AC1 can be a benzoyl halide, a2-alkoxybenzoyl halide, a 3-alkoxybenzoyl halide, a 4-alkoxybenzoylhalide, or 3,5-dialkoxybenzoyl halide; alternatively, a 2-alkoxybenzoylhalide or a 4-alkoxybenzoyl halide; alternatively, a 3-alkoxybenzoylhalide or 3,5-dialkoxybenzoyl halide; alternatively, a 2-alkoxybenzoylhalide; alternatively, 3-alkoxybenzoyl halide; alternatively, a4-alkoxybenzoyl halide; alternatively, 3,5-dialkoxybenzoyl halide. Inother non-limiting embodiments, the acid halide having Structure AC1 canbe a benzoyl halide, a 2-halobenzoyl halide, a 3-halobenzoyl halide, a4-halobenzoyl halide, a 2,6-dihalo-benzoyl halide, or a3,5-dialkylbenzoyl halide; alternatively, a 2-halobenzoyl halide, a4-halobenzoyl halide, or a 2,6-dihalobenzoyl halide; alternatively, a2-halobenzoyl halide or a 4-halobenzoyl halide; alternatively, a3-halobenzoyl halide or a 3,5-dihalobenzoyl halide; alternatively, a2-halobenzoyl halide; alternatively, a 3-halobenzoyl halide;alternatively, a 4-halobenzoyl halide; alternatively, a2,6-dihalo-benzoyl halide; or alternatively, a 3,5-dialkylbenzoylhalide. In other embodiments, the acid halide having Structure AC1 canbe benzoyl chloride, a 2-alkylbenzoyl chloride, a 3-alkylbenzoylchloride, a 4-alkylbenzoyl chloride, a 2,4-dialkylbenzoyl chloride a2,6-dialkylbenzoyl chloride, a 3,5-dialkylbenzoyl chloride, or a2,4,6-trialkylbenzoyl chloride; alternatively, a 2-alkylbenzoylchloride, a 4-alkylbenzoyl chloride, a 2,4-dialkylbenzoyl chloride, a2,6-dialkylbenzoyl chloride, or a 2,4,6-trialkylbenzoyl chloride;alternatively, a 2-alkylbenzoyl chloride or a 4-alkylbenzoyl chloride;alternatively, a 2,4-dialkylbenzoyl chloride a 2,6-dialkylbenzoylchloride; alternatively, a 3-alkylbenzoyl chloride or a3,5-dialkylbenzoyl chloride; alternatively, a 2-alkylbenzoyl chloride ora 2,6-dialkylbenzoyl chloride; alternatively, a 2-alkylbenzoyl chloride;alternatively, a 3-alkylbenzoyl chloride; alternatively, a4-alkylbenzoyl chloride; alternatively, a 2,4-dialkylbenzoyl chloride;alternatively, a 2,6-dialkylbenzoyl chloride; alternatively, a3,5-dialkylbenzoyl chloride; or alternatively, a 2,4,6-trialkylbenzoylchloride. In some other embodiments, the acid halide having StructureAC1 can be benzoyl chloride, a 2-alkoxybenzoyl chloride, a3-alkoxybenzoyl chloride, a 4-alkoxybenzoyl chloride, or a3,5-dialkoxybenzoyl chloride; alternatively, a 2-alkoxybenzoyl chlorideor a 4-alkoxybenzoyl chloride; alternatively, a 3-alkoxybenzoyl chlorideor 3,5-dialkoxybenzoyl chloride; alternatively, a 2-alkoxybenzoylchloride; alternatively, a 3-alkoxybenzoyl chloride; alternatively, a4-alkoxybenzoyl chloride; alternatively, a 3,5-dialkoxybenzoyl chloride.In yet other embodiments, the acid halide having Structure AC1 can bebenzoyl chloride, a 2-halobenzoyl chloride, a 3-halobenzoyl chloride, a4-halobenzoyl chloride, a 2,6-dihalobenzoyl chloride, or a3,5-dialkylbenzoyl chloride; alternatively, a 2-halobenzoyl chloride, a4-halobenzoyl chloride, or a 2,6-dihalobenzoyl chloride; alternatively,a 2-halobenzoyl chloride or a 4-halobenzoyl chloride; alternatively, a3-halobenzoyl chloride or a 3,5-dihalobenzoyl chloride; alternatively, a2-halobenzoyl chloride; alternatively, a 3-halobenzoyl chloride;alternatively, a 4-halobenzoyl chloride; alternatively, a2,6-dihalobenzoyl chloride; or alternatively, a 3,5-dialkylbenzoylchloride.

The halide substituents, alkyl group substituents, and alkoxy groupsubstituents are independently described herein and can be utilized,without limitation, to further describe the alkyl-benzoyl halides oralkylbenzoyl chlorides, dialkylbenzoyl halides or dialkylbenzoylchlorides, trialkyl-benzoyl halides or trialkylbenzoyl chlorides,alkoxybenzoyl halides or alkoxybenzoyl chlorides, dialkoxy-benzoylhalides or dialkoxybenzoyl chlorides, halobenzoyl halides or halobenzoylchlorides, and dihalo-benzoyl halides or dihalobenzoyl chlorides.Generally, the halide substituents, alkyl substituents, or alkoxysubstituents of the dialkylbenzoyl halides or dialkylbenzoyl chlorides,trialkylbenzoyl halides or trialkylbenzoyl chlorides, dialkoxybenzoylhalides or dialkoxybenzoyl chlorides, and dihalobenzoyl halides ordihalobenzoyl chlorides can be the same; or alternatively, the halo,alkyl substituents, or alkoxy substituents of the dialkylbenzoyl halidesor dialkylbenzoyl chlorides, trialkylbenzoyl halides or trialkyl-benzoylchlorides, dialkoxybenzoyl halides or dialkoxybenzoyl chlorides, anddihalobenzoyl halides or dihalobenzoyl chlorides can be different.

In a non-limiting embodiment, the acid halide having Structure AC1 canbe a 2-methyl-benzoyl halide, a 2-ethylbenzoyl halide, a2-isopropylbenzoyl halide, a 2-tert-butylbenzoyl halide, a4-methylbenzoyl halide, a 4-ethylbenzoyl halide, a 4-isopropylbenzoylhalide, or a 4-tert-butylbenzoyl halide; alternatively, a2-methylbenzoyl halide, a 2-ethylbenzoyl halide, a 2-isopropylbenzoylhalide, or a 2-tert-butylbenzoyl halide; alternatively, a4-methylbenzoyl halide a 4-ethylbenzoyl halide, a 4-isopropylbenzoylhalide, or a 4-tert-butylbenzoyl halide; alternatively, a2-methylbenzoyl halide; alternatively, a 2-ethylbenzoyl halide;alternatively, a 2-isopropylbenzoyl halide; alternatively, a2-tert-butylbenzoyl halide; alternatively, a 4-methylbenzoyl halide;alternatively, a 4-ethylbenzoyl halide; alternatively, a4-isopropylbenzoyl halide; or alternatively, a 4-tert-butylbenzoylhalide. In another non-limiting embodiment, the acid halide havingStructure AC1 can be a 2-methoxybenzoyl halide, a 2-ethoxybenzoylhalide, a 2-isoprooxybenzoyl halide, a 2-tert-butoxybenzoyl halide, a4-methoxybenzoyl halide, a 4-ethoxybenzoyl halide, a 4-isoprooxybenzoylhalide, or a 4-tert-butoxybenzoyl halide; alternatively, a2-methoxybenzoyl halide, a 2-ethoxybenzoyl halide, a 2-isoprooxybenzoylhalide, or a 2-tert-butoxybenzoyl halide; alternatively, a4-methoxybenzoyl halide, a 4-ethoxybenzoyl halide, a 4-isoprooxybenzoylhalide, or a 4-tert-butoxybenzoyl halide; alternatively, a2-methoxybenzoyl halide; alternatively, a 2-ethoxybenzoyl halide;alternatively, a 2-isoprooxybenzoyl halide; alternatively, a2-tert-butoxybenzoyl halide; alternatively, a 4-methoxybenzoyl halide;alternatively, a 4-ethoxybenzoyl halide; alternatively, a4-isopropoxybenzoyl halide; or alternatively, a 4-tert-butoxybenzoylhalide. In other non-limiting embodiments, the acid halide havingStructure AC1 can be a 2-fluorobenzoyl halide, a 2-chlorobenzoyl halide,a 3-fluorobenzoyl halide, a 3-chlorobenzoyl halide, a 4-fluorobenzoylhalide, a 4-chlorobenzoyl halide, a 3,5-difluorobenzoyl halide, or a3,5-dichlorobenzoyl halide; alternatively, a 2-fluorobenzoyl halide or a2-chlorobenzoyl halide; alternatively, a 3-fluorobenzoyl halide or a3-chloro-benzoyl halide; alternatively, a 4-fluorobenzoyl halide or a4-chlorobenzoyl halide; alternatively, a 3,5-difluorobenzoyl halide or a3,5-dichlorobenzoyl halide; alternatively, a 3-fluorobenzoyl halide, a3-chlorobenzoyl halide, a 3,5-difluorobenzoyl halide or a3,5-dichlorobenzoyl halide; alternatively, a 3-fluorobenzoyl halide or a3,5-difluorobenzoyl halide; alternatively, a 2-fluorobenzoyl halide;alternatively, a 2-chlorobenzoyl halide; alternatively, a3-fluorobenzoyl halide; alternatively, a 3-chloro-benzoyl halide;alternatively, a 4-fluorobenzoyl halide; alternatively, a4-chlorobenzoyl halide; alternatively, a 3,5-difluorobenzoyl halide; oralternatively, a 3,5-dichlorobenzoyl halide. In other embodiments, theacid halide having Structure AC1 can be 2-methylbenzoyl chloride,2-ethylbenzoyl chloride, 2-isopropylbenzoyl chloride,2-tert-butylbenzoyl chloride, 4-methylbenzoyl chloride, 4-ethyl-benzoylchloride, 4-isopropylbenzoyl chloride, or 4-tert-butylbenzoyl chloride;alternatively, 2-methyl-benzoyl chloride, 2-ethylbenzoyl chloride,2-isopropylbenzoyl chloride, or 2-tert-butylbenzoyl chloride;alternatively, 4-methylbenzoyl chloride, 4-ethylbenzoyl chloride,4-isopropylbenzoyl chloride, or 4-tert-butylbenzoyl chloride;alternatively, 2-methylbenzoyl chloride; alternatively, 2-ethylbenzoylchloride; alternatively, 2-isopropylbenzoyl chloride; alternatively,2-tert-butylbenzoyl chloride; alternatively, 4-methylbenzoyl chloride;alternatively, 4-ethylbenzoyl chloride; alternatively,4-isopropylbenzoyl chloride; or alternatively, 4-tert-butylbenzoylchloride. In some other embodiments, the acid halide having StructureAC1 can be 2-methoxybenzoyl chloride, 2-ethoxybenzoyl chloride,2-isopropoxy-benzoyl chloride, 2-tert-butoxybenzoyl chloride,4-methoxybenzoyl chloride, 4-ethoxybenzoyl chloride, 4-isopropoxybenzoylchloride, or 4-tert-butoxybenzoyl chloride; alternatively,2-methoxybenzoyl chloride, 2-ethoxybenzoyl chloride, 2-isopropoxybenzoylchloride, or 2-tert-butoxybenzoyl chloride; alternatively,4-methoxybenzoyl chloride, 4-ethoxybenzoyl chloride, 4-isopropoxybenzoylchloride, or 4-tert-butoxybenzoyl chloride; alternatively,2-methoxybenzoyl chloride; alternatively, 2-ethoxybenzoyl chloride;alternatively, 2-isopropoxybenzoyl chloride; alternatively,2-tert-butoxybenzoyl chloride; alternatively, 4-methoxybenzoyl chloride;alternatively, 4-ethoxybenzoyl chloride; alternatively,4-isopropoxybenzoyl chloride; or alternatively, 4-tert-butoxybenzoylchloride. In yet other embodiments, the acid halide having Structure AC1can be 2-fluorobenzoyl chloride, 2-chlorobenzoyl chloride,3-fluorobenzoyl chloride, 3-chlorobenzoyl chloride, 4-fluorobenzoylchloride, 4-chlorobenzoyl chloride, 3,5-difluorobenzoyl chloride, or3,5-dichlorobenzoyl chloride; alternatively, 2-fluorobenzoyl chloride or2-chlorobenzoyl chloride; alternatively, 3-fluorobenzoyl chloride or3-chlorobenzoyl chloride; alternatively, 4-fluorobenzoyl chloride or4-chlorobenzoyl chloride; alternatively, 3,5-difluorobenzoyl chloride or3,5-dichlorobenzoyl chloride; alternatively, 3-fluorobenzoyl chloride,3-chlorobenzoyl chloride, 3,5-difluorobenzoyl chloride or3,5-dichlorobenzoyl chloride; alternatively, 3-fluorobenzoyl chloride or3,5-difluorobenzoyl chloride; alternatively, 2-fluorobenzoyl chloride;alternatively, 2-chlorobenzoyl chloride; alternatively, 3-fluorobenzoylchloride; alternatively, 3-chlorobenzoyl chloride; alternatively,4-fluorobenzoyl chloride; alternatively, 4-chlorobenzoyl chloride;alternatively, 3,5-difluorobenzoyl chloride; or alternatively,3,5-dichlorobenzoyl chloride.

In an aspect, L² of the acid halide having Structure AC2 can be any L²described herein. L² is described herein as a feature of theN²-phosphinyl amidine compounds and N²-phosphinyl amidine metal saltcomplexes utilized in various aspects and/or embodiments of thisdisclosure. Since the acid halides having Structure AC2 can be utilizedto prepare N²-phospinyl amidine compounds having Structure NP3, NP8,NP13, and NP18, the aspects and/or embodiments of L² can utilizedwithout limitation to further describe the acid halides having StructureAC2.

In an embodiment, the acid halide having Structure AC2 can be anethanedioyl dihalide, a propanedioyl dihalide, a butanedioyl dihalide, apentanedioyl dihalide, a hexanedioyl dihalide, a heptanedioyl dihalide,an octanedioyl dihalide, a nonanedioyl dihalide, a decanedioyl dihalide,an undecanedioyl dihalide, a dodecanedioyl dihalide, a tridecanedioyldihalide, a tetradecanedioyl dihalide, a pentadecanedioyl dihalide, ahexadecanedioyl dihalide, a heptadecanedioyl dihalide, anoctadecanedioyl dihalide, a nonadecanedioyl dihalide, an eicosanedioyldihalide, or a heneicosanedioyl dihalide; or alternatively, apropanedioyl dihalide, a butanedioyl dihalide, a pentanedioyl dihalide,a hexanedioyl dihalide, a heptanedioyl dihalide, an octanedioyldihalide, a noanedioyl dihalide, a decanedioyl dihalide, anundecanedioyl dihalide, a dodecanedioyl dihalide. In some embodiments,the acid halide having Structure AC2 can be a propanedioyl dihalide, abutanedioyl dihalide, a pentanedioyl dihalide, a hexane-dioyl dihalide,or a heptanedioyl dihalide. In other embodiments, the acid halide havingStructure AC2 can be an ethanedioyl dihalide; alternatively, apropanedioyl dihalide; alternatively, a butanedioyl dihalide;alternatively, a pentanedioyl dihalide; alternatively, a hexanedioyldihalide; alternatively, a heptanedioyl dihalide; alternatively, anoctanedioyl dihalide; alternatively, a noanedioyl dihalide;alternatively, a decanedioyl dihalide; alternatively, an undecanedioyldihalide; alternatively, a dodecane-dioyl dihalide; alternatively, atridecanedioyl dihalide; alternatively, a tetradecanedioyl dihalide;alternatively, a pentadecanedioyl dihalide; alternatively, ahexadecanedioyl dihalide; alternatively, a heptadecanedioyl dihalide;alternatively, an octadecanedioyl dihalide; alternatively, anonadecanedioyl dihalide; alternatively, an eicosanedioyl dihalide; oralternatively, a heneicosanedioyl dihalide. In some embodiments, theacid halide having Structure AC2 can be an ethanedioyl dihalide, apropanedioyl dihalide, an n-butanedioyl dihalide, a 2-methylpropanedioyldihalide, an n-pentanedioyl dihalide, a 2-methylbutanedioyl dihalide, ann-hexanedioyl dihalide, a 2,3-dimethylbutanedioyl dihalide, ann-heptane-dioyl dihalide, a 2,2-dimethylpentanedioyl dihalide, ann-octanedioyl dihalide, or a 2,2,3,3-tetramethyl-butanedioyl dihalide; apropanedioyl dihalide, an n-butanedioyl dihalide, an n-pentanedioyldihalide, an n-hexanedioyl dihalide, an n-heptanedioyl dihalide, or ann-octanedioyl dihalide; alternatively, an ethanedioyl dihalide;alternatively, a propanedioyl dihalide; alternatively, an n-butanedioyldihalide; alternatively, a 2-methylpropanedioyl dihalide; alternatively,an n-pentanedioyl dihalide; alternatively, a 2-methylbutanedioyldihalide; alternatively, an n-hexanedioyl dihalide; alternatively, a2,3-dimethyl-butanedioyl dihalide; alternatively, an n-heptanedioyldihalide; alternatively, a 2,2-dimethylpentanedioyl dihalide;alternatively, an n-octanedioyl dihalide; or alternatively, a2,2,3,3-tetramethylbutanedioyl dihalide. In other embodiments, the acidhalide having Structure AC2 can be ethanedioyl dichloride, propanedioyldichloride, butanedioyl dichloride, pentanedioyl dichloride, hexanedioyldichloride, heptanedioyl dichloride, octanedioyl dichloride, nonanedioyldichloride, decanedioyl dichloride, undecanedioyl dichloride,dodecanedioyl dichloride, tridecanedioyl dichloride, tetradecanedioyldichloride, pentadecanedioyl dichloride, hexadecanedioyl dichloride,heptadecanedioyl dichloride, octadecanedioyl dichloride, nonadecanedioyldichloride, eicosanedioyl dichloride, or heneicosanedioyl dichloride; oralternatively, propanedioyl dichloride, butanedioyl dichloride,pentanedioyl dichloride, hexanedioyl dichloride, heptanedioyldichloride, octanedioyl dichloride, noanedioyl dichloride, decanedioyldichloride, undecanedioyl dichloride, dodecanedioyl dichloride. In someother embodiments, the acid halide having Structure AC2 propanedioyldichloride, butanedioyl dichloride, pentanedioyl dichloride, hexanedioyldichloride, or heptanedioyl dichloride. In yet other embodiments, theacid halide having Structure AC2 can be ethanedioyl dichloride;alternatively, propanedioyl dichloride; alternatively, butanedioyldichloride; alternatively, pentanedioyl dichloride; alternatively,hexanedioyl dichloride; alternatively, heptanedioyl dichloride;alternatively, octanedioyl dichloride; alternatively, noanedioyldichloride; alternatively, decanedioyl dichloride; alternatively,undecanedioyl dichloride; alternatively, dodecanedioyl dichloride;alternatively, tridecanedioyl dichloride; alternatively,tetradecanedioyl dichloride; alternatively, pentadecanedioyl dichloride;alternatively, hexadecanedioyl dichloride; alternatively,heptadecanedioyl dichloride; alternatively, octadecanedioyl dichloride;alternatively, nonadecanedioyl dichloride; alternatively, eicosanedioyldichloride; or alternatively, heneicosanedioyl dichloride. In furtherembodiments, the acid halide having Structure AC2 can be ethanedioyldichloride, propanedioyl dichloride, n-butanedioyl dichloride,2-methylpropanedioyl dichloride, n-pentanedioyl dichloride,2-methylbutanedioyl dichloride, n-hexanedioyl dichloride,2,3-dimethylbutanedioyl dichloride, n-heptanedioyl dichloride,2,2-dimethylpentanedioyl dichloride, n-octanedioyl dichloride, or2,2,3,3-tetramethylbutanedioyl dichloride; alternatively, propanedioyldichloride, n-butanedioyl dichloride, n-pentanedioyl dichloride,n-hexanedioyl dichloride, n-heptanedioyl dichloride, or n-octanedioyldichloride; alternatively, ethanedioyl dichloride; alternatively,propanedioyl dichloride; alternatively, n-butanedioyl dichloride;alternatively, 2-methylpropanedioyl dichloride; alternatively,n-pentanedioyl dichloride; alternatively, 2-methylbutanedioyldichloride; alternatively, n-hexanedioyl dichloride; alternatively,2,3-dimethylbutanedioyl dichloride; alternatively, n-heptanedioyldichloride; alternatively, 2,2-dimethylpentanedioyl dichloride;alternatively, n-octanedioyl dichloride; or alternatively,2,2,3,3-tetramethylbutanedioyl dichloride.

In an aspect, the acid halide having Structure AC2 can have the formulaClC(O)—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—C(O)Cl. R^(1a), R^(2a),R^(3a), R^(4a), and t are described herein as embodiments of an L² grouphaving structure —CR^(1a), R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—. Thedescriptions of R^(1a), R^(2a), R^(3a), R^(4a), and t can be utilizedwithout limitation to further describe the acid halides having theformula ClC(O)—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—C(O)Cl. In anembodiment, the X³ of the acid halide having the structureClC(O)—CR^(1a)R^(2a)(CH₂)_(t)CR^(3a)R^(4a)—C(O)Cl can be a chloride or abromide; alternatively, a chloride; or alternatively, a bromide.

In an embodiment, the acid halide having Structure AC2 can be acyclobutanedicarbonyl-halide, a substituted cyclobutanedicarbonylhalide,a cyclopentanedicarbonylhalide, a substitutedcyclopentanedicarbonylhalide, a cyclohexanedicarbonylhalide, asubstituted cyclohexanedicarbonyl-halide, acycloheptanedicarbonylhalide, a substitutedcycloheptanedicarbonylhalide, a cyclooctane-dicarbonylhalide, or asubstituted cyclooctanedicarbonylhalide. In some embodiments, the acidhalide having Structure AC2 can be a cyclopentanedicarbonylhalide, asubstituted cyclopentanedicarbonyl-halide, acyclohexanedicarbonylhalide, or a substitutedcyclohexanedicarbonylhalide. In other embodiments, the acid halidehaving Structure AC2 can be a cyclobutanedicarbonylhalide or asubstituted cyclobutanedicarbonylhalide; alternatively, acyclopentanedicarbonylhalide or a substitutedcyclopentane-dicarbonylhalide; alternatively, acyclohexanedicarbonylhalide or a substitutedcyclohexanedicarbonyl-halide; alternatively, acycloheptanedicarbonylhalide or a substitutedcycloheptanedicarbonylhalide; or alternatively, acyclooctanedicarbonylhalide or a substitutedcyclooctanedicarbonylhalide. In further embodiments, the acid halidehaving Structure AC2 can be a cyclopentanedicarbonylhalide;alternatively, a substituted cyclopentanedicarbonylhalide; acyclohexanedicarbonylhalide; or alternatively, a substitutedcyclohexanedicarbonylhalide. In other embodiments, the acid halidehaving Structure AC2 can be cyclobutanedicarbonylchloride, a substitutedcyclobutanedicarbonylchloride, cyclopentanedicarbonyl-chloride, asubstituted cyclopentanedicarbonylchloride,cyclohexanedicarbonylchloride, a substitutedcyclohexanedicarbonylchloride, cycloheptanedicarbonylchloride, asubstituted cycloheptanedicarbonyl-chloride,cyclooctanedicarbonylchloride, or a substitutedcyclooctanedicarbonylchloride. In some other embodiments, the acidhalide having Structure AC2 can be cyclopentanedicarbonylchloride, asubstituted cyclopentanedicarbonylchloride,cyclohexanedicarbonylchloride, a substitutedcyclohexanedicarbonyl-chloride. In yet other embodiments, the acidhalide having Structure AC2 can be cyclobutanedicarbonyl-chloride or asubstituted cyclobutanedicarbonylchloride; alternatively,cyclopentanedicarbonylchloride or a substitutedcyclopentanedicarbonylchloride; alternatively,cyclohexanedicarbonylchloride or a substitutedcyclohexanedicarbonylchloride; alternatively,cycloheptanedicarbonylchloride or a substitutedcycloheptanedicarbonylchloride; or alternatively,cyclooctanedicarbonylchloride, or a substitutedcyclooctanedicarbonylchloride. In still further embodiments, the acidhalide having Structure AC2 can be a cyclopentanedicarbonylchloride;alternatively, a substituted cyclopentanedicarbonylchloride;cyclohexanedicarbonylchloride; or alternatively, a substitutedcyclohexanedicarbonylchloride.

In an embodiment, the acid halide having Structure AC2 can be a1,3-cyclopentanedicarbonyl-halide, a substituted1,3-cyclopentanedicarbonylhalide, a 1,3-cyclohexanedicarbonylhalide, asubstituted 1,3-cyclohexanedicarbonylhalide, a1,4-cyclohexanedicarbonylhalide, or a substituted1,4-cyclohexane-dicarbonylhalide; alternatively, a1,3-cyclopentanedicarbonylhalide, a 1,3-cyclohexanedicarbonylhalide, ora 1,4-cyclohexanedicarbonylhalide. In some embodiments, the acid halidehaving Structure AC2 can be a 1,3-cyclopentanedicarbonylhalide or asubstituted 1,3-cyclopentanedicarbonylhalide; alternatively, a1,3-cyclohexanedicarbonylhalide, a substituted1,3-cyclohexanedicarbonylhalide, a 1,3-cyclohexane-dicarbonylhalide, ora substituted 1,4-cyclohexanedicarbonylhalide; alternatively, a1,3-cyclohexane-dicarbonylhalide or a substituted1,3-cyclohexanedicarbonylhalide; alternatively, a1,4-cyclohexane-dicarbonylhalide or a substituted1,4-cyclohexanedicarbonylhalide; alternatively, a1,3-cyclopentane-dicarbonylhalide; alternatively, a1,3-cyclohexanedicarbonylhalide; or alternatively, a1,4-cyclohexane-dicarbonylhalide. In an embodiment, the acid halidehaving Structure AC2 can be 1,3-cyclopentane-dicarbonylchloride, asubstituted 1,3-cyclopentanedicarbonylchloride,1,3-cyclohexanedicarbonyl-chloride, a substituted1,3-cyclohexanedicarbonylchloride, 1,4-cyclohexanedicarbonylchloride, ora substituted 1,4-cyclohexanedicarbonylchloride; alternatively,1,3-cyclopentanedicarbonylchloride, 1,3-cyclohexanedicarbonylchloride,or 1,4-cyclohexanedicarbonylchloride. In some embodiments, the acidhalide having Structure AC2 can be 1,3-cyclopentanedicarbonylchloride ora substituted 1,3-cyclopentanedicarbonylchloride; alternatively,1,3-cyclohexanedicarbonylchloride or a substituted1,3-cyclohexanedicarbonylchloride, 1,3-cyclohexanedicarbonylchloride, ora substituted 1,4-cyclohexane-dicarbonylchloride; alternatively,1,3-cyclohexanedicarbonylchloride or a substituted1,3-cyclohexane-dicarbonylchloride; alternatively,1,4-cyclohexanedicarbonylchloride or a substituted1,4-cyclohexane-dicarbonylchloride; alternatively,1,3-cyclopentanedicarbonylchloride; alternatively,1,3-cyclohexane-dicarbonylchloride; or alternatively,1,4-cyclohexanedicarbonylchloride. L² substituents and substituentpatterns for substituted L² cycloalkane groups are generally disclosedherein and can be utilized without limitation to further describe thesubstituted cycloalkanedicarbonylhalides or substitutedcycloalkane-dicarbonylchlorides which can be utilized as the acid halidehaving Structure AC2 in the various aspects and/or embodiments describedherein.

In an aspect, the acid halide having Structure AC2 can be abi(cyclylcarbonylhalide), a substituted bi(cyclylcarbonylhalide), abis(cyclylcarbonylhalide)methane, a substitutedbis(cyclylcarbonylhalide)methane, a bis(cyclylcarbonylhalide)ethane, ora substituted bis(cyclylcarbonyl-halide)ethane; or alternatively, abis(cyclylcarbonylhalide), a bis(cyclylcarbonylhalide)methane, or abis(cyclylcarbonylhalide)ethane. In an embodiment, the acid halidehaving Structure AC2 can be a bi(cyclylcarbonylhalide) or a substitutedbi(cyclylcarbonylhalide); alternatively,bis(cyclylcarbonyl-halide)methane or a substitutedbis(cyclylcarbonylhalide)methane; or alternatively, abis(cyclylcarbonyl-halide)ethane or a substitutedbis(cyclylcarbonylhalide)ethane. In some embodiments, the acid halidehaving Structure AC2 can be a bi(cyclylcarbonylhalide); alternatively, asubstituted bi(cyclylcarbonyl-halide); alternatively, abis(cyclylcarbonylhalide)methane; alternatively, a substitutedbis(cyclylcarbonyl-halide)methane; alternatively, abis(cyclylcarbonylhalide)ethane; or alternatively, a substitutedbis(cyclyl-carbonylhalide)ethane. In an aspect, the acid halide havingStructure AC2 can be a bi(cyclohexyl-carbonylhalide), a substitutedbi(cyclohexylcarbonylhalide), a bis(cyclohexylcarbonylhalide)methane, asubstituted bis(cyclohexylcarbonylhalide)methane, abis(cyclohexylcarbonylhalide)ethane, or a substitutedbis(cyclohexylcarbonylhalide)ethane; or alternatively, abi(cyclohexylcarbonylhalide), a bis(cyclohexylcarbonylhalide)methane, ora bis(cyclohexylcarbonylhalide)ethane. In an embodiment, the acid halidehaving Structure AC2 can be a bi(cyclohexylcarbonylhalide) or asubstituted bi(cyclohexyl-carbonylhalide); alternatively, abis(cyclohexylcarbonylhalide)methane or a substitutedbis(cyclohexyl-carbonylhalide)methane; or alternatively, abis(cyclohexylcarbonylhalide)ethane or a substitutedbis(cyclohexylcarbonylhalide)ethane. In some embodiments, the acidhalide having Structure AC2 can be a bi(cyclohexylcarbonylhalide);alternatively, a substituted bi(cyclohexylcarbonylhalide);alternatively, a bis(cyclohexylcarbonylhalide)methane; alternatively, asubstituted bis(cyclohexyl-carbonylhalide)methane; alternatively, abis(cyclohexylcarbonylhalide)ethane; or alternatively, a substitutedbis(cyclohexylcarbonylhalide)ethane. In an aspect, the acid halidehaving Structure AC2 can be a bi(cyclylcarbonylchloride), a substitutedbi(cyclylcarbonylchloride), a bis(cyclylcarbonyl-chloride)methane, asubstituted bis(cyclylcarbonylchloride)methane, abis(cyclylcarbonylchloride)ethane, or a substitutedbis(cyclylcarbonylchloride)ethane; or alternatively, abis(cyclylcarbonylchloride), a bis(cyclylcarbonylchloride)methane, or abis(cyclylcarbonylchloride)ethane. In an embodiment, the acid halidehaving Structure AC2 can be a bi(cyclylcarbonylchloride) or asubstituted bi(cyclylcarbonyl-chloride); alternatively,bis(cyclylcarbonylchloride)methane or a substitutedbis(cyclylcarbonyl-chloride)methane; or alternatively, abis(cyclylcarbonylchloride)ethane or a substitutedbis(cyclyl-carbonylchloride)ethane. In some embodiments, the acid halidehaving Structure AC2 can be a bi(cyclylcarbonylchloride); alternatively,a substituted bi(cyclylcarbonylchloride); alternatively, abis(cyclylcarbonylchloride)methane; alternatively, a substitutedbis(cyclylcarbonylchloride)methane; alternatively, abis(cyclylcarbonylchloride)ethane; or alternatively, a substitutedbis(cyclylcarbonyl-chloride)ethane. In other embodiments, the acidhalide having Structure AC2 can be bi(cyclohexyl-carbonylchloride), asubstituted bi(cyclohexylcarbonylchloride),bis(cyclohexylcarbonylchloride)-methane, a substitutedbis(cyclohexylcarbonylchloride)methane,bis(cyclohexylcarbonylchloride)ethane, or a substitutedbis(cyclohexylcarbonylchloride)ethane; or alternatively,bi(cyclohexylcarbonylchloride), bis(cyclohexylcarbonylchloride)methane,or bis(cyclohexylcarbonylchloride)ethane. In some other embodiments, theacid halide having Structure AC2 can be bi(cyclohexylcarbonylchloride)or a substituted bi(cyclohexylcarbonylchloride); alternatively,bis(cyclohexylcarbonylchloride)methane or a substitutedbis(cyclohexylcarbonylchloride)methane; or alternatively,bis(cyclohexylcarbonylchloride)-ethane or a substitutedbis(cyclohexylcarbonylchloride)ethane. In yet other embodiments, theacid halide having Structure AC2 can be bi(cyclohexylcarbonylchloride);alternatively, a substituted bi(cyclohexyl-carbonylchloride);alternatively, bis(cyclohexylcarbonylchloride)methane; alternatively, asubstituted bis(cyclohexylcarbonylchloride)methane; alternatively,bis(cyclohexylcarbonylchloride)ethane; or alternatively, a substitutedbis(cyclohexylcarbonylchloride)ethane. L² substituents and substituentpatterns for substituted L² bicyclylene groups, bis(cyclylene)methanegroups, and bis(cyclylene)ethane groups are generally disclosed hereinand can be utilized without limitation to further describe thesubstituted bi(cyclylcarbonylhalide)s, substitutedbi(cyclylcarbonylchloride)s, substitutedbis(cyclyl-carbonylhalide)methanes, substitutedbis(cyclylcarbonylchloride)methanes, substitutedbis(cyclyl-carbonylhalide)ethanes, and substitutedbis(cyclylcarbonylchloride)ethanes which can be utilized as the acidhalide having Structure AC2 in the various aspects and/or embodimentsdescribed herein.

In an embodiment, the acid halide having Structure AC2 can be a4,4′-bicyclohexyl-dicarbonylhalide, a3,3′-disubstituted-4,4′-bicyclohexyldicarbonylhalide, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldicarbonylhalide, abis(4-cyclohexylcarbonylhalide)methane, abis(3-substituted-4-cyclohexylcarbonylhalide)methane, abis(3,5-disubstituted-4-cyclohexylcarbonylhalide)methane, abis-1,2-(4-cyclohexylcarbonylhalide)ethane, abis-1,2-(3-substituted-4-cyclohexylcarbonylhalide)ethane, abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonylhalide)ethane. In someembodiments, the acid halide having Structure AC2 can be4,4′-bicyclohexyldicarbonylhalide, a3,3′-disubstituted-4,4′-bicyclohexyl-dicarbonylhalide, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldicarbonylhalide;alternatively, a bis(4-cyclohexylcarbonylhalide)methane, abis(3-substituted-4-cyclohexylcarbonylhalide)methane or abis(3,5-disubstituted-4-cyclohexylcarbonylhalide)methane; alternatively,a bis-1,2-(4-cyclohexylcarbonyl-halide)ethane, abis-1,2-(3-substituted-4-cyclohexylcarbonylhalide)ethane or abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonylhalide)ethane. In otherembodiments, the acid halide having Structure AC2 can be a4,4′-bicyclohexyldicarbonylhalide; alternatively, a3,3′-disubstituted-4,4′-bicyclohexyldicarbonyl-halide; alternatively, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldicarbonylhalide;alternatively, a bis(4-cyclohexylcarbonylhalide)methane; alternatively,a bis(3-substituted-4-cyclohexylcarbonylhalide)-methane; alternatively,a bis(3,5-disubstituted-4-cyclohexylcarbonylhalide)methane;alternatively, a bis-1,2-(4-cyclohexylcarbonylhalide)ethane;alternatively, abis-1,2-(3-substituted-4-cyclohexylcarbonyl-halide)ethane; oralternatively, abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonylhalide)ethane. Generally,any bis(cyclohexylcarbonylhalide)ethane disclosed herein (substituted orunsubstituted) can be a bis-1,1-(cyclohexylcarbonylhalide)ethane or abis-1,2-(cyclohexylcarbonylhalide)ethane group; alternatively, abis-1,1-(cyclohexylcarbonylhalide)ethane; or alternatively, abis-1,2-(cyclohexylcarbonyl-halide)ethane. In other embodiments, theacid halide having Structure AC2 can be4,4′-bicyclohexyl-dicarbonylchloride, a3,3′-disubstituted-4,4′-bicyclohexyldicarbonylchloride, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldicarbonylchloride,bis(4-cyclohexylcarbonylchloride)methane, abis(3-substituted-4-cyclohexylcarbonylchloride)methane, abis(3,5-disubstituted-4-cyclohexylcarbonylchloride)methane,bis-1,2-(4-cyclohexylcarbonylchloride)ethane, abis-1,2-(3-substituted-4-cyclohexylcarbonylchloride)ethane, or abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonylchloride)ethane. In someother embodiments, the acid halide having Structure AC2 can be4,4′-bicyclohexyldicarbonylchloride, a3,3′-disubstituted-4,4′-bicyclohexyldicarbonylchloride, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldicarbonylchloride;alternatively, bis(4-cyclohexylcarbonylchloride)methane, abis(3-substituted-4-cyclohexylcarbonyl-chloride)methane or abis(3,5-disubstituted-4-cyclohexylcarbonylchloride)methane; oralternatively, bis-1,2-(4-cyclohexylcarbonylchloride)ethane, abis-1,2-(3-substituted-4-cyclohexylcarbonylchloride)ethane or abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonylchloride)ethane. In yetother embodiments, the acid halide having Structure AC2 can be4,4′-bicyclohexyldicarbonylchloride; alternatively, a3,3′-disubstituted-4,4′-bicyclohexyldicarbonylchloride; alternatively, a3,3′,5,5′-tetrasubstituted-4,4′-bicyclohexyldicarbonylchloride;alternatively, bis(4-cyclohexylcarbonylchloride)methane; alternatively,a bis(3-substituted-4-cyclohexylcarbonylchloride)methane; alternatively,a bis(3,5-disubstituted-4-cyclohexylcarbonylchloride)methane;alternatively, bis-1,2-(4-cyclohexylcarbonylchloride)ethane;alternatively, abis-1,2-(3-substituted-4-cyclohexylcarbonylchloride)ethane; oralternatively, abis-1,2-(3,5-disubstituted-4-cyclohexylcarbonylchloride)ethane.Generally, any bis(cyclohexylcarbonyl-chloride)ethane disclosed herein(substituted or unsubstituted) can be abis-1,1-(cyclohexylcarbonyl-chloride)ethane or abis-1,2-(cyclohexylcarbonylchloride)ethane group; alternatively, abis-1,1-(cyclohexylcarbonylchloride)ethane; or alternatively, abis-1,2-(cyclohexylcarbonylchloride)ethane. Substituents for thesubstituted L² bicyclohex-4,4′-ylene groups,bis(cyclohex-4-ylene)methane groups, and abis-1,2-(cyclohex-4-ylene)ethane groups are generally disclosed hereinand can be utilized without limitation to further describe thesubstituted 4,4′-bicyclohexyldicarbonylhalides, substituted4,4′-bicyclohexyldicarbonychlorides, substitutedbis(4-cyclohexylcarbonylhalide)methanes, substitutedbis(4-cyclohexylcarbonylchloride)methanes, substitutedbis-1,2-(4-cyclohexylcarbonylhalide)ethanes, and substitutedbis-1,2-(4-cyclohexylcarbonylhalide)ethanes which can be utilized as theacid halide having Structure AC2 in the various aspects and/orembodiments described herein.

In an aspect, the acid halide having Structure AC2 can be abenzenedicarbonylhalide or a substituted benzenedicarbonylhalide. In anembodiment, the acid halide having Structure AC2 can be abenzenedicarbonylhalide; or alternatively, a substitutedbenzenedicarbonylhalide. In some embodiments, the acid halide havingStructure AC2 can be a 1,2-benzenedicarbonylhalide or a substituted1,2-benzene-dicarbonylhalide; alternatively, a1,2-benzenedicarbonylhalide; or alternatively, a substituted1,2-benzenedicarbonylhalide. In other embodiments, the acid halidehaving Structure AC2 can be a 1,3-benzenedicarbonylhalide or asubstituted 1,3-benzenedicarbonylhalide; alternatively, a1,3-benzene-dicarbonylhalide; or alternatively, a substituted1,3-benzenedicarbonylhalide. In yet other embodiments, the acid halidehaving Structure AC2 can be a 1,4-benzenedicarbonylhalide or asubstituted 1,4-benzene-dicarbonylhalide; alternatively, a1,4-benzenedicarbonylhalide; or alternatively, a substituted1,4-benzenedicarbonylhalide. In further embodiments, the acid halidehaving Structure AC2 can be a 1,2-benzenedicarbonylhalide, a1,3-benzenedicarbonylhalide, or a 1,4-benzenedicarbonylhalide;alternatively, a 1,3-benzenedicarbonylhalide, or a1,4-benzenedicarbonylhalide. In other embodiments, the acid halidehaving Structure AC2 can be a substituted 1,2-benzenedicarbonylhalide, asubstituted 1,3-benzene-dicarbonylhalide, or a substituted1,4-benzenedicarbonylhalide; alternatively, a substituted1,3-benzene-dicarbonylhalide or a substituted1,4-benzenedicarbonylhalide. In a non-limiting embodiment, the acidhalide having Structure AC2 can be a 2,6-disubstituted1,4-benzenedicarbonylhalide, a 2,3-disubstituted1,4-benzenedicarbonylhalide, a 2,5-disubstituted1,4-benzenedicarbonylhalide, or a 2,3,5,6-tetra-substituted1,4-benzenedicarbonylhalide. In some embodiments, the acid halide havingStructure AC2 can be a 2,6-disubstituted 1,4-benzenedicarbonylhalide ora 2,5-disubstituted 1,4-benzenedicarbonyl-halide; alternatively, a2,6-disubstituted 1,4-benzenedicarbonylhalide; alternatively, a2,3-disubstituted 1,4-benzenedicarbonylhalide; alternatively, a2,5-disubstituted 1,4-benzenedicarbonylhalide; or alternatively, a2,3,5,6-tetrasubstituted 1,4-benzenedicarbonylhalide. In otherembodiments, the acid halide having Structure AC2 can be abenzenedicarbonylchloride or a substituted benzenedicarbonyl-chloride.In an embodiment, the acid halide having Structure AC2 can be abenzenedicarbonylchloride; or alternatively, a substitutedbenzenedicarbonylchloride. In some other embodiments, the acid halidehaving Structure AC2 can be 1,2-benzenedicarbonylchloride or asubstituted 1,2-benzenedicarbonyl-chloride; alternatively,1,2-benzenedicarbonylchloride; or alternatively, a substituted1,2-benzene-dicarbonylchloride. In yet other embodiments, the acidhalide having Structure AC2 can be 1,3-benzenedicarbonylchloride or asubstituted 1,3-benzenedicarbonylchloride; alternatively,1,3-benzene-dicarbonylchloride; or alternatively, a substituted1,3-benzenedicarbonylchloride. In further embodiments, the acid halidehaving Structure AC2 can be 1,4-benzenedicarbonylchloride or asubstituted 1,4-benzenedicarbonylchloride; alternatively,1,4-benzenedicarbonylchloride; or alternatively, a substituted1,4-benzenedicarbonylchloride. In some further embodiments, the acidhalide having Structure AC2 can be 1,2-benzenedicarbonylchloride,1,3-benzenedicarbonylchloride, or 1,4-benzene-dicarbonylchloride;alternatively, 1,3-benzenedicarbonylchloride or1,4-benzenedicarbonylchloride. In yet further embodiments, the acidhalide having Structure AC2 can be a substituted1,2-benzene-dicarbonylchloride, a substituted1,3-benzenedicarbonylchloride, or a substituted1,4-benzenedicarbonyl-chloride; alternatively, a substituted1,3-benzenedicarbonylchloride or a substituted1,4-benzene-dicarbonylchloride. In some non-limiting embodiments, theacid halide having Structure AC2 can be a 2,6-disubstituted1,4-benzenedicarbonylchloride, a 2,3-disubstituted1,4-benzenedicarbonylchloride, a 2,5-disubstituted1,4-benzenedicarbonylchloride, or a 2,3,5,6-tetrasubstituted1,4-benzenedicarbonyl-chloride. In some other embodiments, the acidhalide having Structure AC2 can be a 2,6-disubstituted1,4-benzenedicarbonylchloride or a 2,5-disubstituted1,4-benzenedicarbonylchloride; alternatively, a 2,6-disubstituted1,4-benzenedicarbonylchloride; alternatively, a 2,3-disubstituted1,4-benzenedicarbonyl-chloride; alternatively, a 2,5-disubstituted1,4-benzenedicarbonylchloride; or alternatively, a2,3,5,6-tetrasubstituted 1,4-benzenedicarbonylchloride. L² substituentsand substituent patterns for substituted L² phenylene groups aregenerally disclosed herein and can be utilized without limitation tofurther describe the substituted benzenedicarbonylhalides or substitutedbenzenedicarbonylchlorides which can be utilized as the acid halidehaving Structure AC2 in the various aspects and/or embodiments describedherein.

In an aspect, the acid halide having Structure AC2 can be anaphthalenedicarbonylhalide or a substitutednaphthalenedicarbonylhalide. In an embodiment, the acid halide havingStructure AC2 can be a naphthalenedicarbonylhalide; or alternatively, asubstituted naphthalenedicarbonylhalide. In some embodiments, the acidhalide having Structure AC2 can be a 1,3-naphthalenedicarbonylhalide, asubstituted 1,3-naphthalenedicarbonylhalide, a1,4-naphthalenedicarbonylhalide, a substituted1,4-naphthalenedicarbonylhalide, a 1,5-naphthalenedicarbonylhalide, asubstituted 1,5-naphthalene-dicarbonylhalide, a1,6-naphthalenedicarbonylhalide, a substituted1,6-naphthalenedicarbonylhalide, a 1,7-naphthalenedicarbonylhalide, asubstituted 1,7-naphthalenedicarbonylhalide, a1,8-naphthalenedicarbonylhalide, or a substituted1,8-naphthalenedicarbonylhalide. In other embodiments, the acid halidehaving Structure AC2 can be a 1,3-naphthalenedicarbonylhalide or asubstituted 1,3-naphthalenedicarbonylhalide; alternatively, a1,4-naphthalenedicarbonylhalide or a substituted1,4-naphthalenedicarbonylhalide; alternatively, a1,5-naphthalenedicarbonylhalide or a substituted1,5-naphthalenedicarbonylhalide; alternatively, a1,6-naphthalenedicarbonylhalide or a substituted1,6-naphthalenedicarbonylhalide; alternatively, a1,7-naphthalenedicarbonylhalide or a substituted1,7-naphthalenedicarbonylhalide; or alternatively, a1,8-naphthalenedicarbonylhalide or a substituted1,8-naphthalenedicarbonylhalide. In yet other embodiments, acid halidehaving Structure AC2 can be a 1,3-naphthalenedicarbonylhalide;alternatively, a substituted 1,3-naphthalenedicarbonylhalide;alternatively, a 1,4-naphthalenedicarbonylhalide; alternatively, asubstituted 1,4-naphthalenedicarbonylhalide; alternatively, a1,5-naphthalenedicarbonylhalide; alternatively, a substituted1,5-naphthalenedicarbonyl-halide; alternatively, a1,6-naphthalenedicarbonylhalide; alternatively, a substituted1,6-naphthalenedicarbonylhalide; alternatively, a1,7-naphthalenedicarbonylhalide; alternatively, a substituted1,7-naphthalenedicarbonylhalide; alternatively, a1,8-naphthalenedicarbonylhalide; or alternatively, a substituted1,8-naphthalenedicarbonylhalide. In other embodiments, the acid halidehaving Structure AC2 can be a naphthalenedicarbonylchloride or asubstituted naphthalenedicarbonylchloride. In some other embodiments,the acid halide having Structure AC2 can be anaphthalenedicarbonylchloride; or alternatively, a substitutednaphthalenedicarbonylchloride. In yet other embodiments, the acid halidehaving Structure AC2 can be 1,3-naphthalenedicarbonylchloride, asubstituted 1,3-naphthalene-dicarbonylchloride,1,4-naphthalenedicarbonylchloride, a substituted1,4-naphthalenedicarbonylchloride, 1,5-naphthalenedicarbonylchloride, asubstituted 1,5-naphthalenedicarbonylchloride,1,6-naphthalene-dicarbonylchloride, a substituted1,6-naphthalenedicarbonylchloride, 1,7-naphthalenedicarbonylchloride, asubstituted 1,7-naphthalenedicarbonylchloride,1,8-naphthalenedicarbonylchloride, or a substituted1,8-naphthalenedicarbonylchloride. In further embodiments, the acidhalide having Structure AC2 can be 1,3-naphthalenedicarbonylchloride ora substituted 1,3-naphthalenedicarbonylchloride; alternatively,1,4-naphthalenedicarbonylchloride or a substituted1,4-naphthalenedicarbonylchloride; alternatively,1,5-naphthalenedicarbonylchloride or a substituted1,5-naphthalenedicarbonylchloride; alternatively,1,6-naphthalenedicarbonylchloride or a substituted1,6-naphthalenedicarbonylchloride; alternatively,1,7-naphthalenedicarbonylchloride or a substituted1,7-naphthalenedicarbonylchloride; or alternatively,1,8-naphthalenedicarbonylchloride or a substituted1,8-naphthalenedicarbonylchloride. In yet further embodiments, acidhalide having Structure AC2 can be 1,3-naphthalenedicarbonylchloride;alternatively, a substituted 1,3-naphthalenedicarbonylchloride;alternatively, 1,4-naphthalenedicarbonylchloride; alternatively, asubstituted 1,4-naphthalenedicarbonylchloride; alternatively,1,5-naphthalenedicarbonyl-chloride; alternatively, a substituted1,5-naphthalenedicarbonylchloride; alternatively,1,6-naphthalene-dicarbonylchloride; alternatively, a substituted1,6-naphthalenedicarbonylchloride; alternatively,1,7-naphthalenedicarbonylchloride; alternatively, a substituted1,7-naphthalenedicarbonylchloride; alternatively,1,8-naphthalenedicarbonylchloride; or alternatively, a substituted1,8-naphthalene-dicarbonylchloride. L² substituents and substituentpatterns for substituted L² naphthylene groups are generally disclosedherein and can be utilized without limitation to further describe thesubstituted naphthalenedicarbonylhalides or substitutednaphthalenedicarbonylchlorides which can be utilized as the acid halidehaving Structure AC2 in the various aspects and/or embodiments describedherein.

In an aspect, the acid halide having Structure AC2 can be abi(phenylcarbonylhalide), a substituted bi(phenylcarbonylhalide), abis(phenylcarbonylhalide)methane group, a substitutedbis(phenylcarbonylhalide)methane group, abis(phenylcarbonylhalide)ethane group, or a substitutedbis(phenylcarbonylhalide)ethane group; or alternatively, abi(phenylcarbonylhalide), a bis(phenyl-carbonylhalide)methane group, ora bis(phenylcarbonylhalide)ethane group. In an embodiment, the acidhalide having Structure AC2 can be a bi(phenylcarbonylhalide) or asubstituted bi(phenylcarbonylhalide); alternatively,bis(phenylcarbonylhalide)methane group or a substitutedbis(phenylcarbonylhalide)methane group; or alternatively, abis(phenylcarbonylhalide)ethane group or a substitutedbis(phenylcarbonyl-halide)ethane group. In some embodiments, the acidhalide having Structure AC2 can be a bi(phenyl-carbonylhalide);alternatively, a substituted bi(phenylcarbonylhalide); alternatively, abis(phenylcarbonyl-halide)methane group; alternatively, a substitutedbis(phenylcarbonylhalide)methane group; alternatively, abis(phenylcarbonylhalide)ethane group; or alternatively, a substitutedbis(phenylcarbonylhalide)ethane group.

In other embodiments, the acid halide having Structure AC2 can be abi(phenylcarbonyl-halide), a substituted bi(phenylcarbonylhalide), abis(phenylcarbonylhalide)methane group, a substitutedbis(phenylcarbonylhalide)methane group, abis(phenylcarbonylhalide)ethane group, or a substitutedbis(phenylcarbonylhalide)ethane group; or alternatively, abi(phenylcarbonylhalide), a bis(phenyl-carbonylhalide)methane group, ora bis(phenylcarbonylhalide)ethane group. In some other embodiments, theacid halide having Structure AC2 can be a bi(phenylcarbonylhalide) or asubstituted bi(phenyl-carbonylhalide); alternatively, abis(phenylcarbonylhalide)methane group or a substitutedbis(phenyl-carbonylhalide)methane group; or alternatively, abis(phenylcarbonylhalide)ethane group or a substitutedbis(phenylcarbonylhalide)ethane group. In yet other embodiments, theacid halide having Structure AC2 can be a bi(phenylcarbonylhalide);alternatively, a substituted bi(phenylcarbonylhalide); alternatively, abis(phenylcarbonylhalide)methane group; alternatively, a substitutedbis(phenylcarbonylhalide)methane group; alternatively, abis(phenylcarbonylhalide)ethane group; or alternatively, a substitutedbis(phenylcarbonylhalide)ethane group. In other embodiments, the acidhalide having Structure AC2 can be a bi(phenylcarbonylchloride), asubstituted bi(phenylcarbonylchloride), abis(phenylcarbonylchloride)-methane, a substitutedbis(phenylcarbonylchloride)methane, a bis(phenylcarbonylchloride)ethane,or a substituted bis(phenylcarbonylchloride)ethane; or alternatively, abi(phenylcarbonylchloride), a bis(phenylcarbonylchloride)methane, or abis(phenylcarbonylchloride)ethane group. In some other embodiments, theacid halide having Structure AC2 can be a bi(phenylcarbonylchloride) ora substituted bi(phenylcarbonylchloride); alternatively,bis(phenylcarbonylchloride)methane group or a substitutedbis(phenylcarbonylchloride)methane group; or alternatively, abis(phenylcarbonylchloride)ethane group or a substitutedbis(phenylcarbonylchloride)ethane group. In yet other embodiments, theacid halide having Structure AC2 can be a bi(phenylcarbonylchloride);alternatively, a substituted bi(phenylcarbonyl-chloride); alternatively,a bis(phenylcarbonylchloride)methane group; alternatively, a substitutedbis(phenylcarbonylchloride)methane group; alternatively, abis(phenylcarbonylchloride)ethane group; or alternatively, a substitutedbis(phenylcarbonylchloride)ethane group.

In an embodiment, the acid halide having Structure AC2 can be a2,2′-bi(phenylcarbonyl-halide), a substituted2,2′-bi(phenylcarbonylhalide), a 3,3′-bi(phenylcarbonylhalide), asubstituted 3,3′-bi(phenylcarbonylhalide), a4,4′-bi(phenylcarbonylhalide), or a substituted4,4′-bi(phenylcarbonylhalide); or alternatively, a3,3′-bi(phenylcarbonylhalide), a substituted3,3′-bi(phenylcarbonylhalide), a 4,4′-bi(phenylcarbonylhalide), or asubstituted 4,4′-bi(phenylcarbonylhalide). In some embodiments, the acidhalide having Structure AC2 can be a 2,2′-bi(phenylcarbonylhalide) or asubstituted 2,2′-bi(phenylcarbonylhalide); alternatively, a3,3′-bi(phenylcarbonylhalide) or a substituted3,3′-bi(phenylcarbonylhalide); or alternatively, a4,4′-bi(phenylcarbonylhalide) or a substituted4,4′-bi(phenylcarbonylhalide). In other embodiments, the acid halidehaving Structure AC2 can be a 2,2′-bi(phenylcarbonylhalide);alternatively, a substituted 2,2′-bi(phenylcarbonylhalide);alternatively, a 3,3′-bi(phenylcarbonylhalide); alternatively, asubstituted 3,3′-bi(phenylcarbonylhalide); alternatively, a4,4′-bi(phenylcarbonylhalide); or alternatively, a substituted4,4′-bi(phenylcarbonylhalide). In other embodiments, the acid halidehaving Structure AC2 can be 2,2′-bi(phenylcarbonylchloride), asubstituted 2,2′-bi(phenylcarbonylchloride),3,3′-bi(phenylcarbonylchloride), a substituted3,3′-bi(phenylcarbonyl-chloride), 4,4′-bi(phenylcarbonylchloride), or asubstituted 4,4′-bi(phenylcarbonylchloride); or alternatively,3,3′-bi(phenylcarbonylchloride), a substituted3,3′-bi(phenylcarbonylchloride), 4,4′-bi(phenylcarbonylchloride), or asubstituted 4,4′-bi(phenylcarbonylchloride). In some other embodiments,the acid halide having Structure AC2 can be2,2′-bi(phenylcarbonylchloride) or a substituted2,2′-bi(phenylcarbonylchloride); alternatively,3,3′-bi(phenylcarbonylchloride) or a substituted3,3′-bi(phenylcarbonylchloride); or alternatively,4,4′-bi(phenylcarbonylchloride) or a substituted4,4′-bi(phenylcarbonylchloride). In yet other embodiments, the acidhalide having Structure AC2 can be 2,2′-bi(phenylcarbonylchloride);alternatively, a substituted 2,2′-bi(phenylcarbonylchloride);alternatively, 3,3′-bi(phenylcarbonylchloride); alternatively, asubstituted 3,3′-bi(phenylcarbonyl-chloride); alternatively,4,4′-bi(phenylcarbonylchloride); or alternatively, a substituted4,4′-bi(phenyl-carbonylchloride).

In an embodiment, the acid halide having Structure AC2 can bebis(2-phenylcarbonylhalide)-methane, a substitutedbis(2-phenylcarbonylhalide)methane, abis(3-phenylcarbonylhalide)methane, a substitutedbis(3-phenylcarbonylhalide)methane, abis(4-phenylcarbonylhalide)methane, or a substitutedbis(4-phenylcarbonylhalide)methane; or alternatively, abis(3-phenylcarbonylhalide)methane, a substitutedbis(3-phenylcarbonylhalide)methane, abis(4-phenylcarbonylhalide)methane, or a substitutedbis(4-phenylcarbonylhalide)methane. In some embodiments, the acid halidehaving Structure AC2 can be a bis(2-phenylcarbonylhalide)methane or asubstituted bis(2-phenylcarbonylhalide)methane; alternatively, abis(3-phenylcarbonylhalide)methane or a substitutedbis(3-phenylcarbonylhalide)methane; or alternatively, abis(4-phenylcarbonylhalide)methane or a substitutedbis(4-phenylcarbonylhalide)methane. In other embodiments, the acidhalide having Structure AC2 can be abis(2-phenylcarbonylhalide)-methane; alternatively, a substitutedbis(2-phenylcarbonylhalide)methane; alternatively, abis(3-phenyl-carbonylhalide)methane; alternatively, a substitutedbis(3-phenylcarbonylhalide)methane; alternatively, abis(4-phenylcarbonylhalide)methane; or alternatively, a substitutedbis(4-phenylcarbonylhalide)methane. In some embodiments, the acid halidehaving Structure AC2 can be bis(2-phenylcarbonylchloride)-methane, asubstituted bis(2-phenylcarbonylchloride)methane,bis(3-phenylcarbonylchloride)methane, a substitutedbis(3-phenylcarbonylchloride)methane,bis(4-phenylcarbonylchloride)methane, or a substitutedbis(4-phenylcarbonylchloride)methane; or alternatively,bis(3-phenylcarbonylchloride)-methane, a substitutedbis(3-phenylcarbonylchloride)methane,bis(4-phenylcarbonylchloride)methane, or a substitutedbis(4-phenylcarbonylchloride)methane. In some other embodiments, theacid halide having Structure AC2 can bebis(2-phenylcarbonylchloride)methane or a substitutedbis(2-phenylcarbonyl-chloride)methane; alternatively,bis(3-phenylcarbonylchloride)methane or a substitutedbis(3-phenyl-carbonylchloride)methane; or alternatively,bis(4-phenylcarbonylchloride)methane or a substitutedbis(4-phenylcarbonylchloride)methane. In yet other embodiments, the acidhalide having Structure AC2 can be bis(2-phenylcarbonylchloride)methane;alternatively, a substituted bis(2-phenylcarbonylchloride)-methane;alternatively, bis(3-phenylcarbonylchloride)methane; alternatively, asubstituted bis(3-phenyl-carbonylchloride)methane; alternatively,bis(4-phenylcarbonylchloride)methane; or alternatively, a substitutedbis(4-phenylcarbonylchloride)methane.

In an embodiment, the acid halide having Structure AC2 can bebis(2-phenylcarbonyl-halide)ethane, a substitutedbis(2-phenylcarbonylhalide)ethane, a bis(3-phenylcarbonylhalide)ethane,a substituted bis(3-phenylcarbonylhalide)ethane, abis(4-phenylcarbonylhalide)ethane, or a substitutedbis(4-phenylcarbonylhalide)ethane; or alternatively, abis(3-phenylcarbonylhalide)ethane, a substitutedbis(3-phenylcarbonylhalide)ethane, a bis(4-phenylcarbonylhalide)ethane,or a substituted bis(4-phenylcarbonylhalide)ethane. In some embodiments,the acid halide having Structure AC2 can be abis(2-phenylcarbonylhalide)ethane or a substitutedbis(2-phenylcarbonylhalide)ethane; alternatively, abis(3-phenylcarbonylhalide)ethane or a substitutedbis(3-phenylcarbonylhalide)ethane; or alternatively, abis(4-phenylcarbonylhalide)ethane or a substitutedbis(4-phenylcarbonylhalide)ethane. In other embodiments, the acid halidehaving Structure AC2 can be a bis(2-phenylcarbonylhalide)ethane;alternatively, a substituted bis(2-phenylcarbonylhalide)ethane;alternatively, a bis(3-phenylcarbonyl-halide)ethane; alternatively, asubstituted bis(3-phenylcarbonylhalide)ethane; alternatively, abis(4-phenylcarbonylhalide)ethane; or alternatively, a substitutedbis(4-phenylcarbonylhalide)ethane. In other embodiments, the acid halidehaving Structure AC2 can be bis(2-phenylcarbonylchloride)ethane, asubstituted bis(2-phenylcarbonylchloride)ethane,bis(3-phenylcarbonylchloride)ethane, a substitutedbis(3-phenylcarbonylchloride)ethane,bis(4-phenylcarbonylchloride)ethane, or a substitutedbis(4-phenylcarbonylchloride)ethane; or alternatively,bis(3-phenylcarbonylchloride)ethane, a substitutedbis(3-phenylcarbonylchloride)ethane,bis(4-phenylcarbonylchloride)ethane, or a substitutedbis(4-phenyl-carbonylchloride)ethane. In some other embodiments, theacid halide having Structure AC2 can bebis(2-phenylcarbonylchloride)ethane or a substitutedbis(2-phenylcarbonylchloride)ethane; alternatively,bis(3-phenylcarbonylchloride)ethane or a substitutedbis(3-phenylcarbonylchloride)ethane; or alternatively,bis(4-phenylcarbonylchloride)ethane or a substitutedbis(4-phenylcarbonylchloride)ethane. In yet other embodiments, the acidhalide having Structure AC2 can be bis(2-phenylcarbonylchloride)ethane;alternatively, a substituted bis(2-phenylcarbonylchloride)ethane;alternatively, bis(3-phenylcarbonyl-chloride)ethane; alternatively, asubstituted bis(3-phenylcarbonylchloride)ethane; alternatively,bis(4-phenylcarbonylchloride)ethane; or alternatively, a substitutedbis(4-phenylcarbonylchloride)ethane. Generally, anybis(phenylcarbonylhalide)ethane bis(phenylcarbonylchloride)ethanedisclosed herein (substituted or unsubstituted) can be abis-1,1-(phenylcarbonylhalide)ethane or abis-1,2-(phenyl-carbonylhalide)ethane group(bis-1,1-(phenylcarbonylchloride)ethane or abis-1,2-(phenylcarbonyl-chloride)ethane group); alternatively, abis-1,1-(phenylcarbonylhalide)ethane(bis-1,1-(phenylcarbonyl-chloride)ethane); or alternatively, abis-1,2-(phenylcarbonylhalide)ethane (orbis-1,2-(phenylcarbonyl-chloride)ethane).

In an embodiment, the acid halide having Structure AC2 can be a3,3′-disubstituted-4,4′-bi(phenylcarbonylhalide), a3,3′,5,5′-tetrasubstituted-4,4′-bi(phenylcarbonylhalide), abis(3-substituted-4-phenylcarbonylhalide)methane, abis(3,5-disubstituted-4-phenylcarbonylhalide)methane, abis-1,2-(3-substituted-4-phenylcarbonylhalide)ethane, abis-1,2-(3,5-disubstituted-4-phenylcarbonylhalide)ethane. In someembodiments, the acid halide having Structure AC2 can be a3,3′-disubstituted 4,4′-bi(phenylcarbonylhalide) or a3,3′,5,5′-tetrasubstituted-4,4′-bi(phenylcarbonylhalide); alternatively,a bis(3-substituted-4-phenylcarbonylhalide)methane or abis(3,5-disubstituted-4-phenylcarbonyl-halide)methane; alternatively, abis-1,2-(3-substituted-4-phenylcarbonylhalide)ethane or abis-1,2-(3,5-disubstituted-4-phenylcarbonylhalide)ethane. In otherembodiments, the acid halide having Structure AC2 can be a3,3′-disubstituted-4,4′-bi(phenylcarbonylhalide); alternatively, a3,3′,5,5′-tetra-substituted-4,4′-bi(phenylcarbonylhalide);alternatively, a bis(3-substituted-4-phenylcarbonylhalide)-methane;alternatively, a bis(3,5-disubstituted-4-phenylcarbonylhalide)methane;alternatively, a bis-1,2-(3-substituted-4-phenylcarbonylhalide)ethane;or alternatively, abis-1,2-(3,5-disubstituted-4-phenyl-carbonylhalide)ethane. In some otherembodiments, the acid halide having Structure AC2 can be a3,3′-disubstituted-4,4′-bi(phenylcarbonylchloride), a3,3′,5,5′-tetrasubstituted-4,4′-bi(phenylcarbonyl-chloride), abis(3-substituted-4-phenylcarbonylchloride)methane, abis(3,5-disubstituted-4-phenyl-carbonylchloride)methane, abis-1,2-(3-substituted-4-phenylcarbonylchloride)ethane, abis-1,2-(3,5-disubstituted-4-phenylcarbonylchloride)ethane. In yet otherembodiments, the acid halide having Structure AC2 can be a3,3′-disubstituted 4,4′-bi(phenylcarbonylchloride) or a3,3′,5,5′-tetrasubstituted-4,4′-bi(phenylcarbonylchloride);alternatively, a bis(3-substituted-4-phenylcarbonylchloride)methane or abis(3,5-disubstituted-4-phenylcarbonylchloride)methane; alternatively, abis-1,2-(3-substituted-4-phenyl-carbonylchloride)ethane or abis-1,2-(3,5-disubstituted-4-phenylcarbonylchloride)ethane. In furtherembodiments, the acid halide having Structure AC2 can be a3,3′-disubstituted-4,4′-bi(phenylcarbonyl-chloride); alternatively, a3,3′,5,5′-tetrasubstituted-4,4′-bi(phenylcarbonylchloride);alternatively, a bis(3-substituted-4-phenylcarbonylchloride)methane;alternatively, abis(3,5-disubstituted-4-phenylcarbonyl-chloride)methane; alternatively,a bis-1,2-(3-substituted-4-phenylcarbonylchloride)ethane; oralternatively, abis-1,2-(3,5-disubstituted-4-phenylcarbonylchloride)ethane.

L² substituents and substituent patterns for general and specificsubstituted L² biphenylene groups, bis(phenylene)methane groups, andbis(phenylene)ethane groups are generally disclosed herein and can beutilized without limitation to further describe the general and specificsubstituted bi(phenyl-carbonylhalide)s, substitutedbi(phenylcarbonylchloride)s, substitutedbis(phenylcarbonylhalide)-methanes, substitutedbis(phenylcarbonylchloride)methanes, substitutedbis(phenylcarbonylhalide)-ethanes, and substitutedbis(phenylcarbonylchloride)ethanes which can be utilized as the nitrilehaving Structure N2 in the various aspects and/or embodiments describedherein.

In an embodiment, the acid halide having Structure AC2 can be adi(methylcarbonyl-halide)cycloalkane or a substituteddi(methylcarbonylhalide)cycloalkane; alternatively, adi(methyl-carbonylhalide)cycloalkane;di(methylcarbonylhalide)cycloalkane or a substituteddi(methyl-carbonylhalide)cycloalkane; alternatively, adi(methylcarbonylhalide)cycloalkane. The cycloalkane group of thedi(methylcarbonylhalide)cycloalkanes ordi(methylcarbonylchloride)cycloalkanes (substituted or unsubstituted)can be cyclobutane group, a substituted cyclobutane group, acyclopentane group, a substituted cyclopentane group, a cyclohexanegroup, a substituted cyclohexane group, a cycloheptane group, asubstituted cycloheptane group, a cyclooctane group, or a substitutedcyclooctane group; alternatively, a cyclopentane group, a substitutedcyclopentane group, a cyclohexane group, or a substituted cyclohexanegroup; alternatively, a cyclobutane group or a substituted cyclobutanegroup; alternatively, a cyclopentane group or a substituted cyclopentanegroup; alternatively, a cyclohexane group or a substituted cyclohexanegroup; alternatively, a cycloheptane group or a substitutedcyclo-heptane group; or alternatively, a cyclooctane group, or asubstituted cyclooctane group. In some embodiments, the cycloalkanegroup of the di(methylcarbonylhalide)cycloalkanes ordi(methylcarbonyl-chloride)cycloalkanes (substituted or unsubstituted)can be cyclobutane group, a cyclopentane group, a cyclohexane group, acycloheptane group, or a cyclooctane group; or alternatively, acyclopentane group or a cyclohexane group. In other embodiments, thecycloalkane group of the di(methylcarbonylhalide)-cycloalkanes ordi(methylcarbonylchloride)cycloalkanes (substituted or unsubstituted)can be cyclo-pentane group; alternatively, a substituted cyclopentanegroup; a cyclohexane group; or alternatively, a substituted cyclohexanegroup.

In an embodiment, the acid halide having Structure AC2 can be a1,3-di(methylcarbonyl-halide)cyclopentane, a substituted1,3-di(methylcarbonylhalide)cyclopentane, a1,3-di(methylcarbonyl-halide)cyclohexane, a substituted1,3-di(methylcarbonylhalide)cyclohexane, a1,4-di(methylcarbonyl-halide)cyclohexane, or a substituted1,4-di(methylcarbonylhalide)cyclohexane; alternatively, a1,3-di(methylcarbonylhalide)cyclopentane, a1,3-di(methylcarbonylhalide)cyclohexane, or1,4-di(methyl-carbonylhalide)cyclohexane. In some embodiments, the acidhalide having Structure AC2 can be a1,3-di(methylcarbonylhalide)cyclopentane or a substituted1,3-di(methylcarbonylhalide)cyclopentane; alternatively, a1,3-di(methylcarbonylhalide)cyclohexane or a substituted1,3-di(methylcarbonylhalide)-cyclohexane, a1,4-di(methylcarbonylhalide)cyclohexane or a substituted1,4-di(methylcarbonylhalide)-cyclohexane; alternatively, a1,3-di(methylcarbonylhalide)cyclohexane or a substituted1,3-di(methyl-carbonylhalide)cyclohexane; alternatively, a1,4-di(methylcarbonylhalide)cyclohexane or a substituted1,4-di(methylcarbonylhalide)cyclohexane; alternatively, a1,3-di(methylcarbonylhalide)cyclopentane; alternatively, a1,3-di(methylcarbonylhalide)cyclohexane; or alternatively, a1,4-di(methylcarbonyl-halide)cyclohexane. In other embodiments, the acidhalide having Structure AC2 can be1,3-di(methyl-carbonylchloride)cyclopentane, a substituted1,3-di(methylcarbonylchloride)cyclopentane,1,3-di(methyl-carbonylchloride)cyclohexane, a substituted1,3-di(methylcarbonylchloride)cyclohexane,1,4-di(methyl-carbonylchloride)cyclohexane, or a substituted1,4-di(methylcarbonylchloride)cyclohexane; alternatively,1,3-di(methylcarbonylchloride)cyclopentane,1,3-di(methylcarbonylchloride)cyclohexane, or1,4-di(methylcarbonylchloride)cyclohexane. In some other embodiments,the acid halide having Structure AC2 can be1,3-di(methylcarbonylchloride)cyclopentane or a substituted1,3-di(methyl-carbonylchloride)cyclopentane; alternatively,1,3-di(methylcarbonylchloride)cyclohexane, a substituted1,3-di(methylcarbonylchloride)cyclohexane,1,4-di(methylcarbonylchloride)cyclohexane or a substituted1,4-di(methylcarbonylchloride)cyclohexane; alternatively,1,3-di(methylcarbonylchloride)cyclohexane or a substituted1,3-di(methylcarbonylchloride)cyclohexane; alternatively,1,4-di(methylcarbonylchloride)-cyclohexane or a substituted1,4-di(methylcarbonylchloride)cyclohexane; alternatively,1,3-di(methyl-carbonylchloride)cyclopentane; alternatively, a1,3-di(methylcarbonylchloride)cyclohexane; or alternatively, a1,4-di(methylcarbonylchloride)cyclohexane.

In other embodiments, the acid halide having Structure AC2 can be adi(methylcarbonyl-halide)benzene, or a substituteddi(methylcarbonylhalide)benzene; alternatively, adi(methylcarbonyl-halide) benzene. In some other embodiments, the acidhalide having Structure AC2 can be a1,2-di(methylcarbonylhalide)benzene, a substituted1,2-di(methylcarbonylhalide)benzene, a1,3-di(methylcarbonylhalide)benzene, a substituted1,3-di(methylcarbonylhalide)benzene, a1,4-di(methylcarbonylhalide)benzene, or a substituted1,4-di(methylcarbonylhalide)benzene; alternatively, a1,2-di(methylcarbonylhalide)benzene, a1,3-di(methylcarbonylhalide)benzene, or a1,4-di(methylcarbonylhalide)benzene. In yet other embodiments, the acidhalide having Structure AC2 can be a 1,2-di(methylcarbonylhalide)benzeneor a substituted 1,2-di(methylcarbonylhalide)benzene; alternatively, a1,3-di(methylcarbonylhalide)benzene or a substituted1,3-di(methylcarbonylhalide)-benzene; alternatively, a1,4-di(methylcarbonylhalide)benzene or a substituted1,4-di(methylcarbonyl-halide)benzene; alternatively, a1,2-di(methylcarbonylhalide)benzene; alternatively, a1,3-di(methyl-carbonylhalide)benzene; or alternatively, a1,4-di(methylcarbonylhalide)benzene. In further embodiments, the acidhalide having Structure AC2 can be a di(methylcarbonylchloride)benzeneor a substituted di(methylcarbonylchloride)benzene; or alternatively, adi(methylcarbonylchloride) benzene. In yet further embodiments, the acidhalide having Structure AC2 can be1,2-di(methylcarbonylchloride)-benzene, a substituted1,2-di(methylcarbonylchloride)benzene,1,3-di(methylcarbonylchloride)benzene, a substituted1,3-di(methylcarbonylchloride)benzene,1,4-di(methylcarbonylchloride)benzene, or a substituted1,4-di(methylcarbonylchloride)benzene; alternatively,1,2-di(methylcarbonylchloride)-benzene,1,3-di(methylcarbonylchloride)benzene, or1,4-di(methylcarbonylchloride)benzene. In other embodiments, the acidhalide having Structure AC2 can be 1,2-di(methylcarbonylchloride)benzeneor a substituted 1,2-di(methylcarbonylchloride)benzene; alternatively,1,3-di(methylcarbonylchloride)benzene or a substituted1,3-di(methylcarbonylchloride)benzene; alternatively,1,4-di(methylcarbonylchloride)-benzene or a substituted1,4-di(methylcarbonylchloride)benzene; alternatively,1,2-di(methylcarbonyl-chloride)benzene; alternatively,1,3-di(methylcarbonylchloride)benzene; or alternatively,1,4-di(methyl-carbonylchloride)benzene.

L² substituents for the general and specific substituteddi(methylene)cycloalkane groups and di(methylene)benzene groups aregenerally disclosed herein and can be utilized without limitation tofurther describe the general and specific substituteddi(methylcarbonylhalide)cycloalkanes, substituteddi(methylcarbonylhalide)benzenes, specific substituteddi(methylcarbonylchloride)cycloalkanes, and substituteddi(methylcarbonylchloride)benzenes which can be utilized as the acidhalide having Structure AC2 in the various aspects and/or embodimentsdescribed herein.

In an aspect, the acid halide having Structure AC2 can have StructureAC6, AC7, AC8, AC9, AC10, AC11, AC12, AC13, AC14, AC15, AC16, AC17,AC18, or AC19. In some embodiments, the acid halide having Structure AC2can have Structure AC6, AC7, or AC8; alternatively, AC9, AC10, AC11, orAC12; alternatively, AC13, AC14, or AC15; or alternatively, AC16, AC17,AC18, or AC19. In other embodiments, the acid halide having StructureAC2 can have Structure AC7 or AC8; alternatively, AC9 or AC10;alternatively, AC11 or AC12; alternatively, AC14 or AC15; alternatively,AC16 or AC17; or alternatively, AC18 or AC19. In further embodiments,the acid halide having Structure AC2 can have Structure AC6;alternatively, Structure AC7; alternatively, Structure AC8;alternatively, Structure AC9; alternatively, Structure AC10;alternatively, Structure AC11; alternatively, Structure AC12;alternatively, Structure AC13; alternatively, Structure AC14;alternatively, Structure AC15; alternatively, Structure AC16;alternatively, Structure AC17; alternatively, Structure AC18; oralternatively, Structure AC19.

TABLE 4 Dicarbonylhalides which can be utilized as the acid halidehaving Structure AC2.

Structure AC6

Structure AC7

Structure AC8

Structure AC9

Structure AC10

Structure AC11

Structure AC12

Structure AC13

Structure AC14

Structure AC15

Structure AC16

Structure AC17

Structure AC18

Structure AC19Aspects and embodiments for R^(1L)—R^(11L), R^(21L)—R^(31L),R^(21L′)—R^(31L′), R^(41L)—R^(51L), R^(41L′)—R^(51′), R^(62L)—R^(66L),R^(72L)—R^(76L), R^(72L′)—R^(76L′), R^(82L)—R^(86L), R^(82L′)—R^(86L′),and L^(a), are herein described for L² which can be utilized inN²-phospinyl amidine compounds have Structure NP3, NP8, NP13, or NP18.These aspects and embodiments can be utilized without limitation todescribe the acid halides having Structures AC6-AC19 which can beutilized in the various aspects and/or embodiments described herein. Inan embodiment, the X³ of the acid halide having the Structures AC6-AC19can be a chloride or a bromide; alternatively, a chloride; oralternatively, a bromide.

In a non-limiting embodiment, the acid halide having Structure AC2 canbe a 1,4-benzene-dicarbonylhalide, a2,6-dimethyl-1,4-benzenedicarbonylhalide, a2,6-diethyl-1,4-benzenedicarbonyl-halide, a 2,6-diisopropyl1,4-benzenedicarbonylhalide, a2,6-di-tert-butyl-1,4-benzenedicarbonylhalide, a2,5-dimethyl-1,4-benzenedicarbonylhalide, a2,5-diethyl-1,4-benzenedicarbonylhalide, a2,5-diisopropyl-1,4-benzenedicarbonylhalide, a2,5-di-tert-butyl-1,4-benzenedicarbonylhalide, or a2,3,5,6-tetramethyl-1,4-benzenedicarbonylhalide. In other non-limitingembodiments, the acid halide having Structure AC2 can be a1,4-benzenedicarbonylhalide, a 2,6-dimethyl-1,4-benzenedicarbonylhalide,a 2,6-diethyl-1,4-benzenedicarbonylhalide, a2,6-diisopropyl-1,4-benzenedicarbonylhalide, or a2,6-di-tert-butyl-1,4-benzenedicarbonylhalide; alternatively, a2,5-dimethyl-1,4-benzenedicarbonylhalide, a2,5-diethyl-1,4-benzenedicarbonylhalide, a2,5-diisopropyl-1,4-benzenedicarbonylhalide, or a2,5-di-tert-butyl-1,4-benzenedicarbonylhalide. In yet furthernon-limiting embodiments, the acid halide having Structure AC2 can be a1,4-benzenedicarbonylhalide; alternatively, a2,6-dimethyl-1,4-benzenedicarbonylhalide; alternatively, a2,6-diethyl-1,4-benzenedicarbonylhalide; alternatively, a2,6-diisopropyl-1,4-benzene-dicarbonylhalide; alternatively, a2,6-di-tert-butyl-1,4-benzenedicarbonylhalide; alternatively, a2,5-dimethyl-1,4-benzenedicarbonylhalide; alternatively, a2,5-diethyl-1,4-benzenedicarbonylhalide; alternatively, a2,5-diisopropyl-1,4-benzenedicarbonylhalide; alternatively, a2,5-di-tert-butyl-1,4-benzenedicarbonylhalide; or alternatively, a2,3,5,6-tetramethyl-1,4-benzenedicarbonylhalide. In other embodiments,the acid halide having Structure AC2 can be1,4-benzenedicarbonylchloride,2,6-dimethyl-1,4-benzenedicarbonylchloride,2,6-diethyl-1,4-benzenedicarbonylchloride, 2,6-diisopropyl1,4-benzenedicarbonylchloride,2,6-di-tert-butyl-1,4-benzenedicarbonylchloride,2,5-dimethyl-1,4-benzenedicarbonylchloride,2,5-diethyl-1,4-benzenedicarbonylchloride,2,5-diisopropyl-1,4-benzenedicarbonylchloride,2,5-di-tert-butyl-1,4-benzenedicarbonylchloride, or2,3,5,6-tetramethyl-1,4-benzenedicarbonylchloride. In some otherembodiments, the acid halide having Structure AC2 can be1,4-benzenedicarbonylchloride,2,6-dimethyl-1,4-benzenedicarbonylchloride,2,6-diethyl-1,4-benzene-dicarbonylchloride,2,6-diisopropyl-1,4-benzenedicarbonylchloride, or2,6-di-tert-butyl-1,4-benzene-dicarbonylchloride; alternatively,2,5-dimethyl-1,4-benzenedicarbonylchloride,2,5-diethyl-1,4-benzene-dicarbonylchloride,2,5-diisopropyl-1,4-benzenedicarbonylchloride, or2,5-di-tert-butyl-1,4-benzene-dicarbonylchloride. In yet otherembodiments, the acid halide having Structure AC2 can be1,4-benzene-dicarbonylchloride; alternatively,2,6-dimethyl-1,4-benzenedicarbonylchloride; alternatively,2,6-diethyl-1,4-benzenedicarbonylchloride; alternatively,2,6-diisopropyl-1,4-benzenedicarbonylchloride; alternatively,2,6-di-tert-butyl-1,4-benzenedicarbonylchloride; alternatively,2,5-dimethyl-1,4-benzenedicarbonylchloride; alternatively,2,5-diethyl-1,4-benzenedicarbonylchloride; alternatively,2,5-diisopropyl-1,4-benzenedicarbonylchloride; alternatively,2,5-di-tert-butyl-1,4-benzenedicarbonyl-chloride; or alternatively,2,3,5,6-tetramethyl-1,4-benzenedicarbonylchloride.

In a non-limiting embodiment, the acid halide having Structure AC2 canbe a 3,3′-dimethyl-4,4′-bi(phenylcarbonylhalide), a3,3′-diethyl-4,4′-bi(phenylcarbonylhalide), a3,3′-diisopropyl-4,4′-bi(phenylcarbonylhalide), a3,3′-di-tert-butyl-4,4′-bi(phenylcarbonylhalide), a3,3′,5,5′-tetramethyl-4,4′-bi(phenylcarbonylhalide), a3,3′,5,5′-tetraethyl-4,4′-bi(phenylcarbonylhalide), a3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonylhalide), or a3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenylcarbonylhalide). In someembodiments, the acid halide having Structure AC2 can be a3,3′-dimethyl-4,4′-bi(phenylcarbonyl-halide), a3,3′-diethyl-4,4′-bi(phenylcarbonylhalide), a3,3′-diisopropyl-4,4′-bi(phenylcarbonylhalide), or a3,3′-di-tert-butyl-4,4′-bi(phenylcarbonylhalide); alternatively, a3,3′,5,5′-tetramethyl-4,4′-bi(phenyl-carbonylhalide), a3,3′,5,5′-tetraethyl-4,4′-bi(phenylcarbonylhalide), a3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonylhalide), or a3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenylcarbonylhalide). In otherembodiments, the acid halide having Structure AC2 can be a3,3′-dimethyl-4,4′-bi(phenylcarbonyl-halide); alternatively, a3,3′-diethyl-4,4′-bi(phenylcarbonylhalide); alternatively, a3,3′-diisopropyl-4,4′-bi(phenylcarbonylhalide); alternatively, a3,3′-di-tert-butyl-4,4′-bi(phenylcarbonylhalide); alternatively, a3,3′,5,5′-tetramethyl-4,4′-bi(phenylcarbonylhalide); alternatively, a3,3′,5,5′-tetraethyl-4,4′-bi(phenyl-carbonylhalide); alternatively, a3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonylhalide); oralternatively, a3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenylcarbonylhalide). In otherembodiments, the acid halide having Structure AC2 can be3,3′-dimethyl-4,4′-bi(phenylcarbonylchloride),3,3′-diethyl-4,4′-bi(phenyl-carbonylchloride),3,3′-diisopropyl-4,4′-bi(phenylcarbonylchloride),3,3′-di-tert-butyl-4,4′-bi(phenyl-carbonylchloride),3,3′,5,5′-tetramethyl-4,4′-bi(phenylcarbonylchloride),3,3′,5,5′-tetraethyl-4,4′-bi(phenylcarbonylchloride),3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonylchloride), or3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenylcarbonylchloride). In someother embodiments, the acid halide having Structure AC2 can be3,3′-dimethyl-4,4′-bi(phenylcarbonylchloride),3,3′-diethyl-4,4′-bi(phenylcarbonylchloride),3,3′-diisopropyl-4,4′-bi(phenylcarbonylchloride), or3,3′-di-tert-butyl-4,4′-bi(phenylcarbonylchloride); or alternatively,3,3′,5,5′-tetramethyl-4,4′-bi(phenylcarbonylchloride),3,3′,5,5′-tetraethyl-4,4′-bi(phenyl-carbonylchloride),3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonylchloride), or3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenylcarbonylchloride). In yet otherembodiments, the acid halide having Structure AC2 can be3,3′-dimethyl-4,4′-bi(phenylcarbonylchloride); alternatively,3,3′-diethyl-4,4′-bi(phenylcarbonyl-chloride); alternatively,3,3′-diisopropyl-4,4′-bi(phenylcarbonylchloride); alternatively,3,3′-di-tert-butyl-4,4′-bi(phenylcarbonylchloride); alternatively,3,3′,5,5′-tetramethyl-4,4′-bi(phenylcarbonylchloride); alternatively,3,3′,5,5′-tetraethyl-4,4′-bi(phenylcarbonylchloride); alternatively,3,3′,5,5′-tetraisopropyl-4,4′-bi(phenylcarbonylchloride); oralternatively,3,3′,5,5′-tetra-tert-butyl-4,4′-bi(phenylcarbonyl-chloride).

In a non-limiting embodiment, the acid halide having Structure AC2 canbe a bis(3-methyl-4-phenylcarbonylhalide)methane, abis(3-ethyl-4-phenylcarbonylhalide)methane, abis(3-isopropy-4-phenylcarbonylhalide)methane, abis(3-tert-butyl-4-phenylcarbonylhalide)methane, abis(3,5-dimethyl-4-phenylcarbonylhalide)methane, abis(3,5-diethyl-4-phenylcarbonylhalide)methane, abis(3,5-diisopropy-4-phenylcarbonylhalide)methane, or abis(3,5-di-tert-butyl-4-phenylcarbonylhalide)methane. In someembodiments, the acid halide having Structure AC2 can be abis(3-methyl-4-phenylcarbonyl-halide)methane, abis(3-ethyl-4-phenylcarbonylhalide)methane, abis(3-isopropy-4-phenylcarbonyl-halide)methane, or abis(3-tert-butyl-4-phenylcarbonylhalide)methane; or alternatively, abis(3,5-dimethyl-4-phenylcarbonylhalide)methane, abis(3,5-diethyl-4-phenylcarbonylhalide)methane, abis(3,5-diisopropy-4-phenylcarbonylhalide)methane, or abis(3,5-di-tert-butyl-4-phenylcarbonylhalide)methane. In otherembodiments, the acid halide having Structure AC2 can be abis(3-methyl-4-phenylcarbonyl-halide)methane; alternatively, abis(3-ethyl-4-phenylcarbonylhalide)methane; alternatively, abis(3-isopropy-4-phenylcarbonylhalide)methane; alternatively, abis(3-tert-butyl-4-phenylcarbonylhalide)-methane; alternatively, abis(3,5-dimethyl-4-phenylcarbonylhalide)methane; alternatively, abis(3,5-diethyl-4-phenylcarbonylhalide)methane; alternatively, abis(3,5-diisopropy-4-phenylcarbonylhalide)-methane; or alternatively, abis(3,5-di-tert-butyl-4-phenylcarbonylhalide)methane. In otherembodiments, the acid halide having Structure AC2 can bebis(3-methyl-4-phenylcarbonylchloride)methane,bis(3-ethyl-4-phenylcarbonylchloride)methane,bis(3-isopropy-4-phenylcarbonylchloride)methane,bis(3-tert-butyl-4-phenylcarbonylchloride)methane,bis(3,5-dimethyl-4-phenylcarbonylchloride)methane,bis(3,5-diethyl-4-phenylcarbonylchloride)methane,bis(3,5-diisopropy-4-phenylcarbonylchloride)methane, orbis(3,5-di-tert-butyl-4-phenylcarbonylchloride)methane. In some otherembodiments, the acid halide having Structure AC2 can bebis(3-methyl-4-phenylcarbonylchloride)methane,bis(3-ethyl-4-phenyl-carbonylchloride)methane,bis(3-isopropy-4-phenylcarbonylchloride)methane,bis(3-tert-butyl-4-phenyl-carbonylchloride)methane; or alternatively,bis(3,5-dimethyl-4-phenylcarbonylchloride)methane,bis(3,5-diethyl-4-phenylcarbonylchloride)methane,bis(3,5-diisopropy-4-phenylcarbonylchloride)methane, orbis(3,5-di-tert-butyl-4-phenylcarbonylchloride)methane. In yet otherembodiments, the acid halide having Structure AC2 can bebis(3-methyl-4-phenylcarbonylchloride)methane; alternatively,bis(3-ethyl-4-phenylcarbonylchloride)methane; alternatively,bis(3-isopropy-4-phenylcarbonylchloride)methane; alternatively,bis(3-tert-butyl-4-phenylcarbonylchloride)methane; alternatively,bis(3,5-dimethyl-4-phenylcarbonylchloride)methane; alternatively,bis(3,5-diethyl-4-phenylcarbonylchloride)methane; alternatively,bis(3,5-diisopropy-4-phenylcarbonylchloride)methane; or alternatively,bis(3,5-di-tert-butyl-4-phenylcarbonylchloride)methane.

In a non-limiting embodiment, the acid halide having Structure AC2 canbe a bis(3-methyl-4-phenylcarbonylhalide)ethane, abis(3-ethyl-4-phenylcarbonylhalide)ethane, abis(3-isopropy-4-phenylcarbonylhalide)ethane, abis(3-tert-butyl-4-phenylcarbonylhalide)ethane abis(3,5-dimethyl-4-phenylcarbonylhalide)ethane, abis(3,5-diethyl-4-phenylcarbonylhalide)ethane, abis(3,5-diisopropy-4-phenylcarbonylhalide)ethane, or abis(3,5-di-tert-butyl-4-phenylcarbonylhalide)ethane. In someembodiments, the acid halide having Structure AC2 can be abis(3-methyl-4-phenylcarbonylhalide)ethane, abis(3-ethyl-4-phenylcarbonylhalide)ethane, abis(3-isopropy-4-phenylcarbonylhalide)ethane, abis(3-tert-butyl-4-phenylcarbonylhalide)ethane; alternatively, abis(3,5-dimethyl-4-phenylcarbonylhalide)-ethane, abis(3,5-diethyl-4-phenylcarbonylhalide)ethane, abis(3,5-diisopropy-4-phenylcarbonyl-halide)ethane, or abis(3,5-di-tert-butyl-4-phenylcarbonylhalide)ethane. In otherembodiments, the acid halide having Structure AC2 can be abis(3-methyl-4-phenylcarbonylhalide)ethane; alternatively, abis(3-ethyl-4-phenylcarbonylhalide)ethane; alternatively, abis(3-isopropyl-4-phenylcarbonylhalide)ethane; alternatively, abis(3-tert-butyl-4-phenylcarbonylhalide)ethane; alternatively, abis(3,5-dimethyl-4-phenylcarbonylhalide)ethane; alternatively, abis(3,5-diethyl-4-phenylcarbonylhalide)ethane; alternatively, abis(3,5-diisopropyl-4-phenylcarbonylhalide)ethane; or alternatively, abis(3,5-di-tert-butyl-4-phenylcarbonylhalide)ethane. Generally, thesesubstituted bis(phenylcarbonylhalide)ethanes can be abis-1,1-(phenylcarbonylhalide)ethane or abis-1,2-(phenylcarbonylhalide)ethane group; alternatively, abis-1,1-(phenylcarbonylhalide)ethane; or alternatively, abis-1,2-(phenylcarbonylhalide)ethane.

In other embodiments, the acid halide having Structure AC2 can bebis(3-methyl-4-phenylcarbonylchloride)ethane,bis(3-ethyl-4-phenylcarbonylchloride)ethane,bis(3-isopropyl-4-phenyl-carbonylchloride)ethane,bis(3-tert-butyl-4-phenylcarbonylchloride)ethanebis(3,5-dimethyl-4-phenyl-carbonylchloride)ethane,bis(3,5-diethyl-4-phenylcarbonylchloride)ethane,bis(3,5-diisopropyl-4-phenyl-carbonylchloride)ethane, orbis(3,5-di-tert-butyl-4-phenylcarbonylchloride)ethane. In some otherembodiments, the acid halide having Structure AC2 can bebis(3-methyl-4-phenylcarbonylchloride)-ethane,bis(3-ethyl-4-phenylcarbonylchloride)ethane,bis(3-isopropyl-4-phenylcarbonylchloride)ethane,bis(3-tert-butyl-4-phenylcarbonylchloride)ethane; or alternatively,bis(3,5-dimethyl-4-phenylcarbonyl-chloride)ethane,bis(3,5-diethyl-4-phenylcarbonylchloride)ethane,bis(3,5-diisopropyl-4-phenylcarbonyl-chloride)ethane, orbis(3,5-di-tert-butyl-4-phenylcarbonylchloride)ethane. In yet otherembodiments, the acid halide having Structure AC2 can bebis(3-methyl-4-phenylcarbonylchloride)ethane; alternatively,bis(3-ethyl-4-phenylcarbonylchloride)ethane; alternatively,bis(3-isopropyl-4-phenylcarbonylchloride)-ethane; alternatively,bis(3-tert-butyl-4-phenylcarbonylchloride)ethane; alternatively,bis(3,5-dimethyl-4-phenylcarbonylchloride)ethane; alternatively,bis(3,5-diethyl-4-phenylcarbonylchloride)ethane; alternatively,bis(3,5-diisopropyl-4-phenylcarbonylchloride)ethane; or alternatively,bis(3,5-di-tert-butyl-4-phenylcarbonylchloride)ethane. Generally, thesesubstituted bis(phenylcarbonylchloride)ethanes can bebis-1,1-(phenylcarbonylchloride)ethane orbis-1,2-(phenylcarbonylchloride)ethane group; alternatively,bis-1,1-(phenylcarbonylchloride)ethane; or alternatively,bis-1,2-(phenylcarbonyl-chloride)ethane.

In an aspect, D² of the acid halide having Structure AC3 can be any D²described herein. D² is described herein as a feature of theN²-phosphinyl amidine compounds having Structure NP5, NP10, NP15, orNP20 utilized in various aspects and/or emboidments of this disclosure.Since the acid halide having Structure AC3 can be utilized to prepareembodiments of the N²-phospinyl amidine compounds having Structurehaving Structure NP5, NP10, NP15, or NP20, the aspects and/orembodiments of D² can utilized without limitation to further describethe acid halides having Structure AC3. In an embodiment, any acid halidehaving Structure AC3 described herein can be an acid chloride or an acidbromide, unless explicitly recited otherwise. In some embodiments, theacid halide having Structure AC3 can be an acid chloride; oralternatively, an acid bromide.

Within this disclosure, phosphine halides can be used to ultimatelyprepare the N²-phosphinyl amidine compounds and/or the N²-phosphinylamidine metal salt complexes utilized in various aspects of thisdisclosure. In various embodiments, phosphine halides which can beutilized have Structure PH1.

R⁴ and R⁵ are described as features of N²-phosphinyl amidine compoundshaving Structures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and/or NP20and are described herein. Additionally, X¹ is described herein as afeature of the phosphine halides. Since the phosphine halides areutilized to ultimately prepare embodiments of the N²-phospinyl amidinecompounds having Structures NP1—NP10, NP11, NP13, NP15, NP16, NP18,and/or NP20, X¹, R⁴, and R⁵ can utilized without limitation to furtherdescribe the phosphine halides having Structure PH1.

In an aspect, the phosphine halide can be a diphenylphosphine halide, adialkylphosphine halide, a bis(mono-halo substituted phenyl)phosphinehalide, a bis(mono-alkyl substituted phenyl)phosphine halide, or abis(mono-alkoxy substituted phenyl)phosphine halide; alternatively, adiphenylphosphine halide; alternatively, a dialkylphosphine halide;alternatively, a bis(mono-halo substituted phenyl)phosphine halide;alternatively, a bis(mono-alkyl substituted phenyl)phosphine halide; oralternatively, a bis(mono-alkoxy substituted phenyl)phosphine halide. Inanother aspect, phosphine halide can be an (alkyl)(phenyl)phosphinehalide, a (mono-halo substituted phenyl)(phenyl)phosphine halide, a(mono-alkyl substituted phenyl)(phenyl)phosphine halide, a (mono-alkoxysubstituted phenyl)(phenyl)phosphine halide, a (mono-alkyl substitutedphenyl)(mono-halo substituted phenyl) phosphine halide, or a (mono-alkylsubstituted phenyl)(mono-alkoxy substituted phenyl) phosphine halide;alternatively, (alkyl)(phenyl)phosphine halide; alternatively, a(mono-halo substituted phenyl)(phenyl)phosphine halide; alternatively, a(mono-alkyl substituted phenyl)(phenyl)phosphine halide; alternatively,a (mono-alkoxy substituted phenyl)(phenyl)phosphine halide;alternatively, a (mono-alkyl substituted phenyl)(mono-halo substitutedphenyl) phosphine halide; or alternatively, a (mono-alkyl substitutedphenyl)(mono-alkoxy substituted phenyl) phosphine halide. In anotheraspect, phosphine halide can be a bis(dihalo substitutedphenyl)phosphine halide, a bis(dialkyl substituted phenyl)phosphinehalide, a bis(dialkoxy substituted phenyl)phosphine halide, abis(trialkylphenyl)-phosphine halide, or a bis(trialkoxyphenyl)phosphinehalide; alternatively, a bis(dihalo substituted phenyl)phosphine halide;alternatively, a bis(dialkyl substituted phenyl)phosphine halide;alternatively, a bis(dialkoxy substituted phenyl)phosphine halide;alternatively, a bis(trialkylphenyl)phosphine halide; or alternatively,a bis(trialkoxyphenyl)phosphine halide. Halo, alkyl, and alkoxysubstituents for the substituted phenyl group embodiments of thephosphine halides have been disclosed herein and can be utilized,without limitation to further describe the phosphine halides which canbe utilized in aspects and embodiments described herein.

In a non-limiting aspect, the phosphine halide can be dimethylphosphinechloride, diethylphosphine chloride, diisopropylphosphine chloride,di-tert-butylphosphine chloride, or di-neo-pentylphosphine chloride. Inan embodiment, the phosphine halide can be dimethylphosphine chloride;alternatively, diethylphosphine chloride; alternatively,diisopropylphosphine chloride; alternatively, di-tert-butylphosphinechloride; or alternatively, di-neo-pentylphosphine chloride.

In a non-limiting aspect, the phosphine halide can be(methyl)(phenyl)phosphine chloride, (ethyl)(phenyl)phosphine chloride,(isopropyl)(phenyl)phosphine chloride, (tert-butyl)(phenyl)phosphinechloride, or (neo-pentyl)(phenyl)phosphine chloride. In an embodiment,the phosphine halide can be (methyl)(phenyl)phosphine chloride;alternatively, (ethyl)(phenyl)phosphine chloride; alternatively,(isopropyl)(phenyl)phosphine chloride; alternatively,(tert-butyl)(phenyl)phosphine chloride; or alternatively,(neo-pentyl)(phenyl)phosphine chloride.

In some non-limiting embodiments, the phosphine halide can bedicyclopentylphosphine chloride, dicyclohexylphosphine chloride;alternatively, dicyclopentylphosphine chloride; or alternatively,dicyclohexylphosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can bebis(2-fluorophenyl)-phosphine chloride, bis(2-chlorophenyl)phosphinechloride, bis(3-fluorophenyl)phosphine chloride,bis(3-chlorophenyl)phosphine chloride, bis(4-fluorophenyl)phosphinechloride, or bis(4-chloro-phenyl)phosphine chloride. In someembodiments, the phosphine halide can be bis(2-fluorophenyl)-phosphinechloride, bis(3-fluorophenyl)phosphine chloride, orbis(4-fluorophenyl)phosphine chloride; or alternatively,bis(2-chlorophenyl)phosphine chloride, bis(3-chlorophenyl)phosphinechloride, or bis(4-chlorophenyl)phosphine chloride. In otherembodiments, the phosphine halide can be bis(2-fluoro-phenyl)phosphinechloride; alternatively, bis(2-chlorophenyl)phosphine chloride;alternatively, bis(3-fluorophenyl)phosphine chloride; alternatively,bis(3-chlorophenyl)phosphine chloride; alternatively,bis(4-fluorophenyl)phosphine chloride; or alternatively,bis(4-chlorophenyl)phosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can be(2-fluorophenyl)(phenyl)-phosphine chloride,(2-chlorophenyl)(phenyl)phosphine chloride,(3-fluorophenyl)(phenyl)phosphine chloride,(3-chlorophenyl)(phenyl)phosphine chloride,(4-fluorophenyl)(phenyl)phosphine chloride, or(4-chlorophenyl)(phenyl)phosphine chloride. In some embodiments, thephosphine halide can be (2-fluorophenyl)(phenyl)phosphine chloride,(3-fluorophenyl)(phenyl)phosphine chloride, or(4-fluoro-phenyl)(phenyl)phosphine chloride; or alternatively,(2-chlorophenyl)(phenyl)phosphine chloride,(3-chlorophenyl)(phenyl)phosphine chloride, or(4-chlorophenyl)(phenyl)phosphine chloride. In other embodiments, thephosphine halide can be (2-fluorophenyl)(phenyl)phosphine chloride;alternatively, (2-chlorophenyl)(phenyl)phosphine chloride;alternatively, (3-fluorophenyl)(phenyl)phosphine chloride;alternatively, (3-chlorophenyl)(phenyl)phosphine chloride;alternatively, (4-fluorophenyl)(phenyl)-phosphine chloride; oralternatively, (4-chlorophenyl)(phenyl)phosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can bediphenylphosphine chloride, bis(2-methylphenyl)phosphine chloride,bis(2-ethylphenyl)phosphine chloride, bis(2-isopropyl-phenyl)phosphinechloride, bis(2-tert-butylphenyl)phosphine chloride,bis(3-methylphenyl)phosphine chloride, bis(3-ethylphenyl)phosphinechloride, bis(3-isopropylphenyl)phosphine chloride,bis(3-tert-butylphenyl)phosphine chloride, diphenylphosphine chloride,bis(4-methylphenyl)phosphine chloride, bis(4-ethylphenyl)phosphinechloride, bis(4-isopropylphenyl)phosphine chloride, orbis(4-tert-butylphenyl)phosphine chloride. In an embodiment, thephosphine halide can be bis(2-methyl-phenyl)phosphine chloride,bis(2-ethylphenyl)phosphine chloride, bis(2-isopropylphenyl)phosphinechloride, or bis(2-tert-butylphenyl)phosphine chloride; alternatively,diphenylphosphine chloride, bis(3-methylphenyl)phosphine chloride,bis(3-ethylphenyl)phosphine chloride, bis(3-isopropylphenyl)-phosphinechloride, or bis(3-tert-butylphenyl)phosphine chloride; oralternatively, diphenylphosphine chloride, bis(4-methylphenyl)phosphinechloride, bis(4-ethylphenyl)phosphine chloride,bis(4-isopropyl-phenyl)phosphine chloride, orbis(4-tert-butylphenyl)phosphine chloride. In other embodiments, thephosphine halide can be diphenylphosphine chloride; alternatively,bis(2-methylphenyl)phosphine chloride; alternatively,bis(2-ethylphenyl)phosphine chloride; alternatively,bis(2-isopropylphenyl)-phosphine chloride; alternatively,bis(2-tert-butylphenyl)phosphine chloride; alternatively,bis(3-methyl-phenyl)phosphine chloride; alternatively,bis(3-ethylphenyl)phosphine chloride; alternatively,bis(3-isopropylphenyl)phosphine chloride; alternatively,bis(3-tert-butylphenyl)phosphine chloride; alternatively,diphenylphosphine chloride; alternatively, bis(4-methylphenyl)phosphinechloride; alternatively, bis(4-ethylphenyl)phosphine chloride,bis(4-isopropylphenyl)phosphine chloride; or alternatively,bis(4-tert-butylphenyl)phosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can bediphenylphosphine chloride, (2-methylphenyl)(phenyl)phosphine chloride,(2-ethylphenyl)(phenyl)phosphine chloride,(2-isopropylphenyl)(phenyl)phosphine chloride,(2-tert-butylphenyl)(phenyl)phosphine chloride,(3-methylphenyl)(phenyl)phosphine chloride,(3-ethylphenyl)(phenyl)phosphine chloride,(3-isopropyl-phenyl)(phenyl)phosphine chloride,(3-tert-butylphenyl)(phenyl)phosphine chloride, diphenylphosphinechloride, (4-methylphenyl)(phenyl)phosphine chloride,(4-ethylphenyl)(phenyl)phosphine chloride,(4-isopropylphenyl)(phenyl)phosphine chloride, or(4-tert-butylphenyl)(phenyl)phosphine chloride. In an embodiment, thephosphine halide can be (2-methylphenyl)(phenyl)phosphine chloride,(2-ethylphenyl)-(phenyl)phosphine chloride,(2-isopropylphenyl)(phenyl)phosphine chloride, or(2-tert-butylphenyl)-(phenyl)phosphine chloride; alternatively,diphenylphosphine chloride, (3-methylphenyl)(phenyl)-phosphine chloride,(3-ethylphenyl)(phenyl)phosphine chloride,(3-isopropylphenyl)(phenyl)phosphine chloride, or(3-tert-butylphenyl)(phenyl)phosphine chloride; or alternatively,diphenylphosphine chloride, (4-methylphenyl)(phenyl)phosphine chloride,(4-ethylphenyl)(phenyl)phosphine chloride,(4-isopropyl-phenyl)(phenyl)phosphine chloride, or(4-tert-butylphenyl)(phenyl)phosphine chloride. In other embodiments,the phosphine halide can be diphenylphosphine chloride; alternatively,(2-methylphenyl)-(phenyl)phosphine chloride; alternatively,(2-ethylphenyl)(phenyl)phosphine chloride; alternatively,(2-isopropylphenyl)(phenyl)phosphine chloride; alternatively,(2-tert-butylphenyl)(phenyl)phosphine chloride; alternatively,(3-methylphenyl)(phenyl)phosphine chloride; alternatively,(3-ethylphenyl)-(phenyl)phosphine chloride; alternatively,(3-isopropylphenyl)(phenyl)phosphine chloride; alternatively,(3-tert-butylphenyl)(phenyl)phosphine chloride; alternatively,diphenylphosphine chloride; alternatively,(4-methylphenyl)(phenyl)phosphine chloride; alternatively,(4-ethylphenyl)(phenyl)phosphine chloride,(4-isopropylphenyl)(phenyl)phosphine chloride; or alternatively,(4-tert-butylphenyl)(phenyl)phosphine chloride.

In yet another non-limiting aspect, the phosphine halide can bediphenylphosphine chloride, bis(2-methoxyphenyl)phosphine chloride,bis(2-ethoxyphenyl)phosphine chloride, bis(2-isopropoxy-phenyl)phosphinechloride, bis(2-tert-butoxyphenyl)phosphine chloride,bis(3-methoxyphenyl)phosphine chloride, bis(3-ethoxyphenyl)phosphinechloride, bis(3-isopropoxyphenyl)phosphine chloride,bis(3-tert-butoxyphenyl)phosphine chloride, diphenoxyphosphine chloride,bis(4-methoxyphenyl)-phosphine chloride, bis(4-ethoxyphenyl)phosphinechloride, bis(4-isopropoxyphenyl)phosphine chloride, orbis(4-tert-butoxyphenyl)phosphine chloride. In an embodiment, thephosphine halide can be bis(2-methoxyphenyl)phosphine chloride,bis(2-ethoxyphenyl)phosphine chloride, bis(2-isopropoxy-phenyl)phosphinechloride, or bis(2-tert-butoxyphenyl)phosphine chloride; alternatively,diphenoxy-phosphine chloride, bis(3-methoxyphenyl)phosphine chloride,bis(3-ethoxyphenyl)phosphine chloride, bis(3-isopropoxyphenyl)phosphinechloride, or bis(3-tert-butoxyphenyl)phosphine chloride; oralternatively, diphenoxyphosphine chloride,bis(4-methoxyphenyl)phosphine chloride, bis(4-ethoxy-phenyl)phosphinechloride, bis(4-isopropoxyphenyl)phosphine chloride, orbis(4-tert-butoxyphenyl)-phosphine chloride. In other embodiments, thephosphine halide can be diphenylphosphine chloride; alternatively,bis(2-methoxyphenyl)phosphine chloride; alternatively,bis(2-ethoxyphenyl)phosphine chloride; alternatively,bis(2-isopropoxyphenyl)phosphine chloride; alternatively,bis(2-tert-butoxy-phenyl)phosphine chloride; alternatively,bis(3-methoxyphenyl)phosphine chloride; alternatively,bis(3-ethoxyphenyl)phosphine chloride; alternatively,bis(3-isopropoxyphenyl)phosphine chloride; alternatively,bis(3-tert-butoxyphenyl)phosphine chloride; alternatively,diphenoxyphosphine chloride; alternatively,bis(4-methoxyphenyl)phosphine chloride; alternatively,bis(4-ethoxyphenyl)phosphine chloride, bis(4-isopropoxyphenyl)phosphinechloride; or alternatively, bis(4-tert-butoxyphenyl)phosphine chloride.

In yet another non non-limiting aspect, the phosphine halide can bediphenylphosphine chloride, (2-methoxyphenyl)(phenyl)phosphine chloride,(2-ethoxyphenyl)(phenyl)phosphine chloride,(2-isopropoxyphenyl)(phenyl)phosphine chloride,(2-tert-butoxyphenyl)(phenyl)phosphine chloride,(3-methoxyphenyl)(phenyl)phosphine chloride,(3-ethoxyphenyl)(phenyl)phosphine chloride,(3-isopropoxyphenyl)(phenyl)phosphine chloride,(3-tert-butoxyphenyl)(phenyl)phosphine chloride, diphenoxyphosphinechloride, (4-methoxyphenyl)(phenyl)phosphine chloride,(4-ethoxyphenyl)-(phenyl)phosphine chloride,(4-isopropoxyphenyl)(phenyl)phosphine chloride, or(4-tert-butoxyphenyl)-(phenyl)phosphine chloride. In an embodiment, thephosphine halide can be (2-methoxyphenyl)(phenyl)-phosphine chloride,(2-ethoxyphenyl)(phenyl)phosphine chloride,(2-isopropoxyphenyl)(phenyl)-phosphine chloride, or(2-tert-butoxyphenyl)(phenyl)phosphine chloride; alternatively,diphenoxy-phosphine chloride, (3-methoxyphenyl)(phenyl)phosphinechloride, (3-ethoxyphenyl)(phenyl)phosphine chloride,(3-isopropoxyphenyl)(phenyl)phosphine chloride, or(3-tert-butoxyphenyl)(phenyl)phosphine chloride; or alternatively,diphenoxyphosphine chloride, (4-methoxyphenyl)(phenyl)phosphinechloride, (4-ethoxyphenyl)(phenyl)phosphine chloride,(4-isopropoxyphenyl)(phenyl)phosphine chloride, or(4-tert-butoxyphenyl)(phenyl)phosphine chloride. In other embodiments,the phosphine halide can be diphenylphosphine chloride; alternatively,(2-methoxyphenyl)(phenyl)phosphine chloride; alternatively,(2-ethoxyphenyl)(phenyl)phosphine chloride; alternatively,(2-isopropoxyphenyl)(phenyl)phosphine chloride; alternatively,(2-tert-butoxyphenyl)(phenyl)phosphine chloride; alternatively,(3-methoxy-phenyl)(phenyl)phosphine chloride; alternatively,(3-ethoxyphenyl)(phenyl)phosphine chloride; alternatively,(3-isopropoxyphenyl)(phenyl)phosphine chloride; alternatively,(3-tert-butoxyphenyl)-(phenyl)phosphine chloride; alternatively,diphenoxyphosphine chloride; alternatively,(4-methoxy-phenyl)(phenyl)phosphine chloride; alternatively,(4-ethoxyphenyl)(phenyl)phosphine chloride,(4-isopropoxyphenyl)(phenyl)phosphine chloride; or alternatively,(4-tert-butoxyphenyl)(phenyl)-phosphine chloride.

Within this disclosure, halogenated compounds can be used to prepare theN²-phosphinyl amidine compounds and/or the N²-phosphinyl amidine metalsalt complexes utilized in various aspects of this disclosure. Invarious embodiments, the halogenated compounds which can be utilized canhave Structure HC1. R³ is described as a feature of N²-phosphinylamidine having Structures NP1—NP10, NP11, NP13, NP15, NP16, NP18, and/orNP20.

X²R³  Structure HC1

Since the halogenated HC1 is utilized to ultimately prepare embodimentsof the N²-phospinyl amidine compounds having Structures NP1—NP10, NP11,NP13, NP15, NP16, NP18, and/or NP20, the R³ description can be utilizedwithout limitation to further describe the halogenated compound havingStructure HC1. Generally, X² of Structure HC1 represents a halide. In anembodiment, X² of the halogenated compound can be fluoride, chloride,bromide, or iodide; alternatively, fluoride; alternatively, chloride;alternatively, bromide; or alternatively, iodide.

In an aspect, the halogenated compound having Structure HC1 can be amethylhalide, an ethylhalide, a propylhalide, a butylhalide, apentylhalide, a hexylhalide, a heptylhalide, an octylhalide, anonylhalide, a decylhalide, a undecylhalide, a dodecylhalide, atridecylhalide, a tetradecylhalide, a pentadecylhalide, ahexadecylhalide, a heptadecylhalide, an octadecylhalide, or anonadecylhalide; or alternatively, a methylhalide, an ethylhalide, apropylhalide, a butylhalide, a pentylhalide, a hexylhalide, aheptylhalide, an octylhalide, a nonylhalide, or a decylhalide. In someembodiments, the halogenated compound having Structure HC1 can be amethylhalide, an ethylhalide, an n-propylhalide, an iso-propylhalide,butylhalide, an iso-butylhalide, a sec-butylhalide, a tert-butylhalide,an n-pentylhalide, an iso-pentylhalide, a sec-pentylhalide, or anneopentylhalide; alternatively, a methylhalide, an ethyl-halide, aniso-propylhalide, a tert-butylhalide, or a neopentylhalide;alternatively, a methylhalide; alternatively, an ethylhalide;alternatively, an n-propylhalide; alternatively, an iso-propylhalide;alternatively, a tert-butylhalide; or alternatively, a neopentylhalide.

In an aspect, the halogenated compound having Structure HC1 can be acyclobutylhalide, a substituted cyclobutylhalide, a cyclopentylhalide, asubstituted cyclopentylhalide, a cyclohexylhalide, a substitutedcyclohexylhalide, a cycloheptylhalide, a substituted cycloheptylhalide,a cyclooctylhalide, or a substituted cyclooctylhalide. In an embodimentthe halide having Structure HC1 can be a cyclopentylhalide, asubstituted cyclopentylhalide, a cyclohexylhalide, or a substitutedcyclohexylhalide. In other embodiments, the halogenated compound havingStructure HC1 can be a cyclobutylhalide or a substitutedcyclobutylhalide; alternatively, a cyclopentylhalide or a substitutedcyclopentylhalide; alternatively, a cyclohexylhalide or a substitutedcyclohexylhalide; alternatively, a cycloheptylhalide or a substitutedcycloheptylhalide; or alternatively, a cyclooctylhalide, or asubstituted cyclooctylhalide. In further embodiments, the halogenatedcompound having Structure HC1 can be a cyclopentylhalide; alternatively,a substituted cyclopentylhalide; a cyclohexylhalide; or alternatively, asubstituted cyclohexylhalide. Substituents and substituents patterns forthe R¹ cycloalkyl groups are described herein and can be utilizedwithout limitation to further describe the substituted cycloalkylhalideswhich can be utilized in aspects and embodiments described herein.

In various embodiments, the halogenated compounds which can be utilizedcan have Structure HC2. R^(11c), R^(12c), R^(13c), R^(14c), and R

R^(15c) substituents, substituent patterns, and n for the R³ grouphaving Structure G5 are described herein and can be utilized withoutlimitation to describe halogenated compound having Structure HC2 whichcan be utilized in the various aspects and/or embodiments describedherein. In an embodiment, X² of the halogenated compound havingStructure HC2 can be fluoride, chloride, bromide, or iodide;alternatively, fluoride; alternatively, chloride; alternatively,bromide; or alternatively, iodide.

In an aspect, the halogenated compound can be a benzylhalide or asubstituted benzylhalide. In an embodiment, the halogenated compound canbe a benzylhalide; or alternatively, a substituted benzyl halide.

Various aspect and embodiments described herein refer non-hydrogensubstituents such as halogen (or halo, halide), hydrocarbyl,hydrocarboxy, alkyl, and/or alkoxy substituents. The non-hydrogensubstituents of any aspect or embodiment calling for a substituent canbe a halide, a C₁ to C₁₀ hydrocarbyl group, or a C₁ to C₁₀ hydrocarboxygroup; alternatively, a halide or a C₁ to C₁₀ hydrocarbyl group;alternatively, a halide or a C₁ to C₁₀ hydrocarboxy group;alternatively, a C₁ to C₁₀ hydrocarbyl group or a C₁ to C₁₀ hydrocarboxygroup; alternatively, a halide; alternatively, a C₁ to C₁₀ hydrocarbylgroup; or alternatively, a C₁ to C₁₀ hydrocarboxy group. In otherembodiments, the non-hydrogen substituents of any aspect or embodimentcalling for a substituent can be a halide, a C₁ to C₅ hydrocarbyl group,or a C₁ to C₅ hydrocarboxy group; alternatively, a halide or a C₁ to C₅hydrocarbyl group; alternatively, a halide or a C₁ to C₅ hydrocarboxygroup; alternatively, a C₁ to C₅ hydrocarbyl group or a C₁ to C₅hydrocarboxy group; alternatively, a halide; alternatively, a C₁ to C₅hydrocarbyl group; or alternatively, a C₁ to C₅ hydrocarboxy group.

In an embodiment, any halide substituent of any aspect or embodimentcalling for a substituent can be a fluoride, chloride, bromide, oriodide; alternatively, a fluoride or chloride. In some embodiments, anyhalide substituent of any aspect or embodiment calling for a substituentcan be a fluoride; alternatively, a chloride; alternatively, a bromide;or alternatively, an iodide.

In an embodiment, any hydrocarbyl substituent can be an alkyl group, anaryl group, or an aralkyl group; alternatively, an alkyl group;alternatively, an aryl group; or alternatively, an aralkyl group. In anembodiment, any alkyl substituent of any aspect or embodiment callingfor a substituent can be a methyl group, an ethyl group, an n-propylgroup, an isopropyl group, an n-butyl group, a sec-butyl group, anisobutyl group, a tert-butyl group, an n-pentyl group, a 2-pentyl group,a 3-pentyl group, a 2-methyl-1-butyl group, a tert-pentyl group, a3-methyl-1-butyl group, a 3-methyl-2-butyl group, or a neo-pentyl group;alternatively, a methyl group, an ethyl group, an isopropyl group, atert-butyl group, or a neo-pentyl group; alternatively, a methyl group;alternatively, an ethyl group; alternatively, an isopropyl group;alternatively, a tert-butyl group; or alternatively, a neo-pentyl group.In an embodiment, any aryl substituent of any aspect or embodimentcalling for a substituent can be phenyl group, a tolyl group, a xylylgroup, or a 2,4,6-trimethylphenyl group; alternatively, a phenyl group;alternatively, a tolyl group; alternatively, a xylyl group; oralternatively, a 2,4,6-trimethylphenyl group. In an embodiment, anyaralkyl substituent of any aspect or embodiment calling for asubstituent can be benzyl group or an ethylphenyl group(2-phenyleth-1-yl or 1-phenyleth-1-yl); alternatively, a benzyl group;alternatively, an ethylphenyl group; alternatively, a 2-phenyleth-1-ylgroup; or alternatively, a 1-phenyleth-1-yl group.

In an embodiment, any hydrocarboxy substituent of any aspect orembodiment calling for a substituent can be an alkoxy group, an aryloxygroup, or an aralkoxy group; alternatively, an alkoxy group;alternatively, an aryloxy group, or an aralkoxy group. In an embodiment,any alkoxy substituent of any aspect or embodiment calling for asubstituent can be a methoxy group, an ethoxy group, an n-propoxy group,an isopropoxy group, an n-butoxy group, a sec-butoxy group, an isobutoxygroup, a tert-butoxy group, an n-pentoxy group, a 2-pentoxy group, a3-pentoxy group, a 2-methyl-1-butoxy group, a tert-pentoxy group, a3-methyl-1-butoxy group, a 3-methyl-2-butoxy group, or a neo-pentoxygroup; alternatively, a methoxy group, an ethoxy group, an isopropoxygroup, a tert-butoxy group, or a neo-pentoxy group; alternatively, amethoxy group; alternatively, an ethoxy group; alternatively, anisopropoxy group; alternatively, a tert-butoxy group; or alternatively,a neo-pentoxy group. In an embodiment, any aryloxy substituent of anyaspect or embodiment calling for a substituent can be phenoxy group, atoloxy group, a xyloxy group, or a 2,4,6-trimethylphenoxy group;alternatively, a phenoxy group; alternatively, a toloxy group;alternatively, a xyloxy group; or alternatively, a2,4,6-trimethylphenoxy group. In an embodiment, any aralkoxy substituentof any aspect or embodiment calling for a substituent can be benzoxygroup.

The methods described herein can utilize one or more solvents. Solventwhich can be utilized in aspects of the present disclosure includewithout limitation water, hydrocarbons, halogenated hydrocarbons,ethers, carbonates, esters, ketones, aldehydes, alcohols, nitriles andcombinations thereof. In some embodiments, an aspect of the inventionmay call for a polar solvent. Polar solvents which can be utilizedinclude without limitation water ethers, carbonates, esters, ketones,aldehydes, alcohols, nitriles, and mixtures thereof; alternatively,ethers, carbonates, esters, ketones, aldehydes, alcohols, nitriles, andmixtures thereof; alternatively, ethers, esters, ketones, alcohols,nitriles, and mixtures thereof; alternatively, ethers; alternatively,carbonates; alternatively, esters; alternatively, ketones;alternatively, aldehydes; alternatively, alcohols; or alternatively,nitriles. In some embodiments, an aspect of the invention may call foran aprotic polar solvent. Aprotic polar solvents which can be utilizedinclude without limitation ethers, esters, ketones, aldehydes, nitriles,and mixtures thereof; alternatively, ethers, nitriles and mixturesthereof; alternatively, esters, ketones, aldehydes and mixtures thereof;alternatively, ethers; alternatively, esters; alternatively, ketones;alternatively, aldehydes; or alternatively, nitriles. In otherembodiments, an aspect of the disclosure may call for a non-polarsolvent. Non-polar solvents include without limitation hydrocarbons,halogenated hydrocarbons, or mixtures thereof; alternatively, ahydrocarbon; or alternatively, a halogenated hydrocarbon. In anotherembodiment, an aspect of the present disclosure may call for a solventthat is substantially unreactive with a metal alkyl. Solvents which areunreactive with a metal alkyl include without limitation ethers,hydrocarbons, and mixtures thereof; alternatively, ethers; oralternatively, hydrocarbons.

Hydrocarbons and halogenated hydrocarbon can include, for example,aliphatic hydrocarbons, aromatic hydrocarbons, petroleum distillates,halogenated aliphatic hydrocarbons, halogenated aromatic hydrocarbons,or combinations thereof; alternatively, aliphatic hydrocarbons, aromatichydrocarbons, halogenated aliphatic hydrocarbons, halogenated aromatichydrocarbons, and combinations thereof; alternatively, aliphatichydrocarbons; alternatively, aromatic hydrocarbons; alternatively,halogenated aliphatic hydrocarbons; or alternatively, halogenatedaromatic hydrocarbons. Aliphatic hydrocarbons which can be useful as asolvent include C₃ to C₂₀ aliphatic hydrocarbons; alternatively, C₄ toC₁₅ aliphatic hydrocarbons; or alternatively, C₅ to C₁₀ aliphatichydrocarbons. The aliphatic hydrocarbons can be cyclic or acyclic and/orcan be linear or branched, unless otherwise specified. Non-limitingexamples of suitable acyclic aliphatic hydrocarbon solvents that can beutilized singly or in any combination include propane, iso-butane,n-butane, butane (n-butane or a mixture of linear and branched C₄acyclic aliphatic hydrocarbons), pentane (n-pentane or a mixture oflinear and branched C_(s) acyclic aliphatic hydrocarbons), hexane(n-hexane or mixture of linear and branched C₆ acyclic aliphatichydrocarbons), heptane (n-heptane or mixture of linear and branched C₇acyclic aliphatic hydrocarbons), octane (n-octane or a mixture of linearand branched C₈ acyclic aliphatic hydrocarbons), and combinationsthereof; alternatively, iso-butane, n-butane, butane (n-butane or amixture of linear and branched C₄ acyclic aliphatic hydrocarbons),pentane (n-pentane or a mixture of linear and branched C₅ acyclicaliphatic hydrocarbons), hexane (n-hexane or mixture of linear andbranched C₆ acyclic aliphatic hydrocarbons), heptane (n-heptane ormixture of linear and branched C₇ acyclic aliphatic hydrocarbons),octane (n-octane or a mixture of linear and branched C₈ acyclicaliphatic hydrocarbons), and combinations thereof; alternatively,iso-butane, n-butane, butane (n-butane or a mixture of linear andbranched C₄ acyclic aliphatic hydrocarbons), pentane (n-pentane or amixture of linear and branched C₅ acyclic aliphatic hydrocarbons),heptane (n-heptane or mixture of linear and branched C₇ acyclicaliphatic hydrocarbons), octane (n-octane or a mixture of linear andbranched C₈ acyclic aliphatic hydrocarbons), and combinations thereof;alternatively, propane; alternatively, iso-butane; alternatively,n-butane; alternatively, butane (n-butane or a mixture of linear andbranched C₄ acyclic aliphatic hydrocarbons); alternatively, pentane(n-pentane or a mixture of linear and branched C₅ acyclic aliphatichydrocarbons); alternatively, hexane (n-hexane or mixture of linear andbranched C₆ acyclic aliphatic hydrocarbons); alternatively, heptane(n-heptane or mixture of linear and branched C₇ acyclic aliphatichydrocarbons); or alternatively, octane (n-octane or a mixture of linearand branched C₈ acyclic aliphatic hydrocarbons). Non-limiting examplesof suitable cyclic aliphatic hydrocarbon solvents include cyclohexane,methyl cyclohexane; alternatively, cyclohexane; or alternatively,methylcyclohexane. Aromatic hydrocarbons which can be useful as asolvent include C₆ to C₂₀ aromatic hydrocarbons; or alternatively, C₆ toC₁₀ aromatic hydrocarbons. Non-limiting examples of suitable aromatichydrocarbons that can be utilized singly or in any combination includebenzene, toluene, xylene (including ortho-xylene, meta-xylene,para-xylene, or mixtures thereof), and ethylbenzene, or combinationsthereof; alternatively, benzene; alternatively, toluene; alternatively,xylene (including ortho-xylene, meta-xylene, para-xylene or mixturesthereof); or alternatively, ethylbenzene.

Halogenated aliphatic hydrocarbons which can be useful as a solventinclude C₁ to C₁₅ halogenated aliphatic hydrocarbons; alternatively, C₁to C₁₀ halogenated aliphatic hydrocarbons; or alternatively, C₁ to C₅halogenated aliphatic hydrocarbons. The halogenated aliphatichydrocarbons can be cyclic or acyclic and/or can be linear or branched,unless otherwise specified. Non-limiting examples of suitablehalogenated aliphatic hydrocarbons which can be utilized includemethylene chloride, chloroform, carbon tetrachloride, dichloroethane,trichloroethane, and combinations thereof; alternatively, methylenechloride, chloroform, dichloroethane, trichloroethane, and combinationsthereof; alternatively, methylene chloride; alternatively, chloroform;alternatively, carbon tetrachloride; alternatively, dichloroethane; oralternatively, trichloroethane. Halogenated aromatic hydrocarbons whichcan be useful as a solvent include C₆ to C₂₀ halogenated aromatichydrocarbons; or alternatively, C₆ to C₁₀ halogenated aromatichydrocarbons. Non-limiting examples of suitable halogenated aromatichydrocarbons include chlorobenzene, dichlorobenzene, and combinationsthereof; alternatively, chlorobenzene and dichlorobenzene.

Ethers, carbonates, esters, ketones, aldehydes, or alcohols which can beuseful as a solvent include C₂ to C₂₀ ethers, carbonates, esters,ketones, aldehydes, or alcohols; alternatively, C₂ to C₁₀ ethers,carbonates, esters, ketones, aldehydes, or alcohols; or alternatively,C₂ to C₅ ethers, carbonates, esters, ketones, aldehydes, or alcohols.Suitable ether solvents can be cyclic or acyclic. Non-limiting examplesof suitable ethers which can be useful as a solvent include dimethylether, diethyl ether, methyl ethyl ether, monoethers or diethers ofglycols (e.g., dimethyl glycol ether), furans, substituted furans,dihydrofuran, substituted dihydrofurans, tetrahydrofuran (THF),substituted tetrahydrofurans, tetrahydropyrans, substitutedtetrahydropyrans, 1,3-dioxanes, substituted 1,3-dioxanes, 1,4-dioxanes,substituted 1,4-dioxanes, or mixtures thereof. In an embodiment, eachsubstituent of a substituted furan, substituted dihydrofuran,substituted tetrahydrofuran, substituted tetrahydropyran, substituted1,3-dioxane, or substituted 1,4-dioxane, can be a C₁ to C₅ alkyl group.C₁ to C₅ alkyl substituent group are disclosed herein and can beutilized without limitation of further describe the substitutedtetrahydrofuran, dihydrofuran, furan, 1,3-dioxane, or 1,4 dioxanesolvents. Non-limiting examples of suitable carbonates which can beutilized as a solvent include ethylene carbonate, propylene carbonate,diethyl carbonate, diethyl carbonate, glycerol carbonate, andcombinations thereof. Non-limiting examples of suitable esters which canbe utilized as a solvent include ethyl acetate, propyl acetate, butylacetate, isobutyl isobutyrate, methyl lactate, ethyl lactate, andcombinations thereof. Non-limiting examples of suitable ketones whichcan be utilized as a solvent include acetone, ethyl methyl ketone,methyl isobutyl ketone, and combinations thereof. Non-limiting examplesof suitable alcohols which can be utilized as a solvent includemethanol, ethanol, propanol, isopropanol, n-butanol, isobutanol,pentanol, hexanol, heptanol, octanol, benzyl alcohol, phenol,cyclohexanol, and the like, or combinations thereof.

For the purpose of any U.S. national stage filing from this application,all publications and patents mentioned in this disclosure areincorporated herein by reference in their entireties, for the purpose ofdescribing and disclosing the constructs and methodologies described inthose publications, which might be used in connection with the methodsof this disclosure. Any publications and patents discussed above andthroughout the text are provided solely for their disclosure prior tothe filing date of the present application. Nothing herein is to beconstrued as an admission that the inventors are not entitled toantedate such disclosure by virtue of prior invention.

Unless indicated otherwise, when a range of any type is disclosed orclaimed, for example a range of the number of carbon atoms, molarratios, temperatures, and the like, it is intended to disclose or claimindividually each possible number that such a range could reasonablyencompass, including any sub-ranges encompassed therein. For example,when describing a range of the number of carbon atoms, each possibleindividual integral number and ranges between integral numbers of atomsthat the range includes are encompassed therein. Thus, by disclosing aC₁ to C₁₀ alkyl group or an alkyl group having from 1 to 10 carbon atomsor “up to” 10 carbon atoms, Applicants' intent is to recite that thealkyl group can have 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms, andthese methods of describing such a group are interchangeable. Whendescribing a range of measurements such as molar ratios, every possiblenumber that such a range could reasonably encompass can, for example,refer to values within the range with one significant digit more than ispresent in the end points of a range. In this example, a molar ratiobetween 1.03:1 and 1.12:1 includes individually molar ratios of 1.03:1,1.04:1, 1.05:1, 1.06:1, 1.07:1, 1.08:1, 1.09:1, 1.10:1, 1.11:1, and1.12:1. Applicants' intent is that these two methods of describing therange are interchangeable. Moreover, when a range of values is disclosedor claimed, which Applicants intent to reflect individually eachpossible number that such a range could reasonably encompass, Applicantsalso intend for the disclosure of a range to reflect, and beinterchangeable with, disclosing any and all sub-ranges and combinationsof sub-ranges encompassed therein. In this aspect, Applicants'disclosure of a C₁ to C₁₀ alkyl group is intended to literally encompassa C₁ to C₆ alkyl, a C₄ to C₈ alkyl, a C₂ to C₇ alkyl, a combination of aC₁ to C₃ and a C₅ to C₇ alkyl, and so forth. When describing a range inwhich the end points of the range have different numbers of significantdigits, for example, a molar ratio from 1:1 to 1.2:1, every possiblenumber that such a range could reasonably encompass can, for example,refer to values within the range with one significant digit more than ispresent in the end point of a range having the greatest number ofsignificant digits, in this case 1.2:1. In this example, a molar ratiofrom 1:1 to 1.2:1 includes individually molar ratios of 1.01, 1.02,1.03, 1.04, 1.05, 1.06, 1.07, 1.08, 1.09, 1.10, 1.11, 1.12, 1.13, 1.14,1.15, 1.16, 1.17, 1.18, 1.19, and 1.20, all relative to 1, and any andall sub-ranges and combinations of sub-ranges encompassed therein.Accordingly, Applicants reserve the right to proviso out or exclude anyindividual members of any such group, including any sub-ranges orcombinations of sub-ranges within the group, if for any reasonApplicants choose to claim less than the full measure of the disclosure,for example, to account for a reference that Applicants are unaware ofat the time of the filing of the application.

In any application before the United States Patent and Trademark Office,the Abstract of this application is provided for the purpose ofsatisfying the requirements of 37 C.F.R. §1.72 and the purpose stated in37 C.F.R. §1.72(b) “to enable the United States Patent and TrademarkOffice and the public generally to determine quickly from a cursoryinspection the nature and gist of the technical disclosure.” Therefore,the Abstract of this application is not intended to be used to construethe scope of the claims or to limit the scope of the subject matter thatis disclosed herein. Moreover, any headings that can be employed hereinare also not intended to be used to construe the scope of the claims orto limit the scope of the subject matter that is disclosed herein. Anyuse of the past tense to describe an example otherwise indicated asconstructive or prophetic is not intended to reflect that theconstructive or prophetic example has actually been carried out.

The present disclosure is further illustrated by the following examples,which are not to be construed in any way as imposing limitations uponthe scope thereof. On the contrary, it is to be clearly understood thatresort can be had to various other aspects, embodiments, modifications,and equivalents thereof which, after reading the description herein, cansuggest themselves to one of ordinary skill in the art without departingfrom the spirit of the present invention or the scope of the appendedclaims.

The data and descriptions provided in the following examples are givento show particular aspects and embodiments of the compounds, catalystsystems, and olefin oligomerization and/or olefin polymerization methodsdisclosed, and to demonstrate a number of the practices and advantagesthereof. The examples are given as a more detailed demonstration of someof the aspects and embodiments described herein and are not intended tolimit the disclosure or claims in any manner.

EXAMPLES Synthesis of Amidine Compounds

Amines, nitriles, and n-butyl lithium were utilized as obtained from thechemical supplier. The solvents were dried and/or purified usingconventional methods and stored under conditions to limit their abilityto pick-up water. The syntheses of the amidine compounds were performedusing standard air-free procedures and techniques.

Table 7 provides the amines and nitriles utilized in amidine syntheses1-9 along with the produced amidine compounds.

Amidine Synthesis 1—N¹-(2,6-dimethylphenyl)benzamidine (Amidine I)

2,6-dimethylaniline (6.15 mL, 50.0 mmol) was added to 100 mL ofdiethylether and cooled to 0° C. Butyllithium (26.0 mL of 2.0 M solutionin diethylether, 52.0 mmol) was added dropwise to the cooled anilinesolution, affording an off-white solid after complete addition. Theslurry was warmed to room temperature and stirred for 2 hours.Benzonitrile (5.2 mL, 51.0 mmol) was added slowly resulting in theformation of a suspended yellow-orange solid after complete addition.Stirring was continued for 1 hour and the solvent was removed in vacuo.Tetrahydrofuran (150 mL) was added and the mixture was refluxedovernight under argon, yielding a dark orange-red solution. Distilledwater (2.0 mL, 112 mmol) was added and the mixture became a milky yellowsolution after stirring for 30 minutes at room temperature. Solid,presumably lithium hydroxide, was removed via aerobic filtration and theremaining solvent was removed in vacuo, to produce a light yellow solid.The solid was slurried in 80 mL of pentane and stirred for 2 hours.Filtration of the slurry yielded 10.28 g (92%) of white solid. ¹H NMR(400 MHz, CDCl₃): 7.93 (d, 2H), 7.48 (m, 3H), 7.06 (d, 2H), 6.90 (t, 1H), 4.58 (s, 2H), 2.17 (s, 6H).

Amidine Synthesis 2—N¹-(2,6-diisopropylphenyl)benzamidine (Amidine II)

Procedure as described for Amidine I using the following amounts: 8.50mL of 2,6-diisopropylaniline (45.0 mmol); 23.5 mL of 2.0 M butyllithium(47.0 mmol); 4.70 mL of benzonitrile (46.0 mmol). Filtration of thefinal pentane solution yielded 6.31 g (50%) of white solid. ¹H NMR (400MHz, CDCl₃): 7.92 (d, 2H), 7.48 (m, 3H), 7.17 (d, 2H), 7.09 (t, 1 H),4.59 (s, 2H), 3.06 (septet, 2H), 1.20 (d, 12H).

Amidine Synthesis 3—4-methyl-N¹-(2,6-dimethylphenyl)benzamidine (AmidineIII)

Procedure as described for Amidine I using the following amounts: 6.15mL of 2,6-dimethylaniline (50.0 mmol); 25.0 mL of 2.0 M butyllithium(50.0 mmol), 5.86 g of 4-methylbenzonitrile (50.0 mmol). After refluxingovernight, the solution was deep red. Addition of water yielded a yellowsolution with suspended solid. Solution was filtered, taken to dryness,resuspended in 100 mL of pentane and stirred vigorously for 1 hour. Theresulting white solid was filtered, washed with 10 mL of pentane anddried in vacuo yielding 11.19 g (90%) of white powder. ¹H NMR (400 MHz,CDCl₃): 7.83 (d, 2H), 7.26 (d, 2H), 7.05 (d, 2H), 6.89 (t, 1H), 4.54 (s,2H), 2.42 (s, 3H), 2.15 (s, 6H).

Amidine Synthesis 4—4-tert-butyl-N¹-(2,6-dimethylphenyl)benzamidine(Amidine IV)

Procedure as described for Amidine I using the following amounts: 6.15mL of 2,6-dimethylaniline (50.0 mmol); 26.0 mL of 2.0 M butyllithium(52.0 mmol), 8.50 mL of 4-t-butylbenzonitrile (50.0 mmol). Afterrefluxing overnight, the solution was red-orange. Addition of wateryielded a yellow solution with suspended solid. Solution was filtered,taken to dryness, resuspended in 100 mL of pentane and stirredvigorously for 1 hour. The resulting white solid was filtered and driedin vacuo yielding 11.19 g of white powder. The filtrate was concentratedto approximately 50 mL and cooled to −10° C. An additional 1.47 g ofsolid was isolated. Total yield 10.60 g (76%). ¹H NMR (400 MHz, CDCl₃):7.87 (d, 2H), 7.50 (d, 2H), 7.04 (d, 2H), 6.90 (t, 1H), 4.56 (s, 2H),2.15 (s, 6H), 1.36 (s, 9H). ¹³C {¹H} NMR (100 MHz, CDCl₃): 154.27,153.01, 146.97, 133.12, 129.16, 128.53, 126.83, 125.88, 123.05, 35.21,31.59, 18.17.

Amidine Synthesis 5—N¹-(2-isopropyl-6-methylphenyl)-4-methylbenzamidine(Amidine V)

Procedure as described for Amidine I using the following amounts: 7.80mL of 2-isopropyl-6-methylaniline (50.0 mmol); 25.0 mL of 2.0 Mbutyllithium (50.0 mmol), 5.86 g of 4-methylbenzonitrile (50.0 mmol).After refluxing overnight, the solution was dark brown. Addition ofwater yielded an orange-brown solution with suspended solid. Solutionwas filtered and taken to dryness. The residue was treated with 100 mLof pentane stirred overnight and filtered yielding 10.98 g (83%) ofbeige material. ¹H NMR (400 MHz, CDCl₃): 7.82 (d, 2H), 7.26 (d, 2H),7.15 (d, 1H), 7.05 (d, 1H), 6.98 (t, 1 H), 4.56 (s, 2H), 3.09 (septet,1H), 2.42 (s, 3H), 2.15 (s, 3H), 1.21 (d, 3H), 1.16 (d, 3H).

Amidine Synthesis 6—N¹-(2-tert-butylphenyl)-4-methylbenzamidine (AmidineVI)

Procedure as described for Amidine I using the following amounts: 7.80mL of 2-t-butylaniline (50.0 mmol); 25.0 mL of 2.0 M butyllithium (50.0mmol), 5.86 g of 4-methylbenzonitrile (50.0 mmol). After refluxingovernight, the solution was dark brown. Addition of water yielded anorange solution with suspended solid. Solution was filtered and taken todryness. The residue was treated with 75 mL of pentane, stirredovernight, and filtered yielding 11.14 g (84%) of off-white material. ¹HNMR (400 MHz, CDCl₃): 7.82 (d, 2H), 7.41 (d, 1H), 7.27 (d, 2H), 7.17 (t,1H), 7.00 (t, 1H), 6.82 (d, 1 H), 4.75 (s, 2H), 2.42 (s, 3H), 1.40 (s,9H).

Amidine Synthesis 7—4-tert-butyl-N¹-(2-tert-butylphenyl)benzamidine(Amidine VII)

Procedure as described for Amidine I using the following amounts: 7.80mL of 2-t-butylaniline (50.0 mmol); 25.0 mL of 2.0 M butyllithium (50.0mmol), 8.50 ml of 4-t-butylbenzonitrile (50.0 mmol). After refluxingovernight, the solution was dark brown. Addition of water yielded anorange solution with suspended solid. Solution was filtered and taken todryness. The residue was treated with 75 mL of pentane, stirred for 30minutes, and filtered yielding 13.43 g (87%) of light orange solid. ¹HNMR (400 MHz, CDCl₃): 7.87 (d, 2H), 7.49 (d, 2H), 7.41 (d, 1H), 7.17 (t,1H), 7.00 (t, 1H), 6.81 (d, 1 H), 4.75 (s, 2H), 1.41 (s, 9H), 1.36 (s,9H).

Amidine Synthesis 8—N¹-(2-ethylphenyl)-4-methylbenzamidine (AmidineVIII)

Procedure as described for Amidine I using the following amounts: 6.18mL of 2-ethylaniline (50.0 mmol); 25.0 mL of 2.0 M butyllithium (50.0mmol), 5.86 g of 4-methylbenzonitrile (50.0 mmol). After refluxingovernight, the solution was dark brown. Addition of water yielded ayellow solution with suspended solid. Solution was filtered and taken todryness. The residue was treated with 75 mL of pentane, stirredovernight, and filtered yielding 10.51 g (88%) of light yellow solid. ¹HNMR (400 MHz, CDCl₃): 7.79 (d, 2H), 7.25 (d, 3H), 7.17 (t, 1H), 7.02 (t,1H), 6.86 (d, 1 H), 4.68 (s, 2H), 2.57 (q, 2H), 2.41 (s, 3H), 1.17 (t,3H).

Amidine Synthesis 9—4-methyl-N¹-phenylbenzamidine (Amidine IX)

Procedure as described for Amidine I using the following amounts: 4.60mL of aniline (50.0 mmol); 25.0 mL of 2.0 M butyllithium (50.0 mmol),5.86 g of 4-methylbenzonitrile (50.0 mmol). After refluxing overnight,the solution was orange. Addition of water yielded a yellow solutionwith suspended solid. Solution was filtered and taken to dryness. Theresidue was treated with 50 mL of pentane, stirred for 30 minutes, andfiltered yielding 8.23 g (78%) of light yellow solid. ¹H NMR (400 MHz,CDCl₃): 7.76 (d, 2H), 7.36 (t, 2H), 7.25 (d, 2H), 7.06 (t, 1H), 6.98 (d,2 H), 4.79 (s, 2H), 2.40 (s, 3H).

Amidine Synthesis 10—N¹-(2-isopropylphenyl)-4-methylbenzamidine (AmidineX)

2-isopropylaniline (5.0 mL, 36.1 mmol) was added to 100 mL ofdiethylether and cooled to 0° C. Butyllithium (18.0 mL of 2.0 M solutionin pentane, 36.1 mmol) was added dropwise to the cooled anilinesolution, affording a light yellow suspension after complete addition.The slurry was warmed to room temperature and stirred for 2 hours.Toluonitrile (4.23 g, 36.1 mmol) was added slowly resulting in theformation of a bright yellow solution after complete addition. Stirringwas continued for 1 hour and the solvent was removed in vacuo.Tetrahydrofuran (150 mL) was added and the mixture was refluxedovernight under argon, yielding a dark orange-brown solution. Distilledwater (2.0 mL, 112 mmol) was added and the mixture became a milky yellowsolution after stirring for 30 minutes at room temperature. Solid,presumably lithium hydroxide, was removed via aerobic filtration and theremaining solvent was removed in vacuo, to produce a light yellow solid.The solid was slurried in 50 mL of pentane and stirred for 2 hours.Filtration of the slurry yielded 7.56 g (83%) of light yellow solid. ¹HNMR (400 MHz, CDCl₃): 7.77 (d, 2H), 7.30 (d, 1H), 7.22 (d, 2H), 7.15 (t,1H), 7.04 (t, 1H), 6.83 (d, 1 H), 4.70 (s, 2H), 3.16 (septet, 1H), 2.40(s, 3H), 1.19 (d, 6H).

Amidine Synthesis 11—N¹-(2-n-propylphenyl)-4-methylbenzamidine (AmidineXI)

Procedure as described for Amidine X using the following amounts: 6.00mL of 2-n-propylaniline (42.6 mmol); 21.3 mL of 2.0 M butyllithium (42.6mmol); 5.00 g of toluonitrile (42.6 mmol). Filtration of the finalpentane solution yielded 9.53 g (89%) of light yellow solid. ¹H NMR (400MHz, CDCl₃): 7.76 (d, 2H), 7.22 (m, 3H), 7.15 (t, 1H), 6.99 (t, 1 H),6.84 (d, 1 H), 4.69 (s, 2H), 2.51 (t, 2H), 2.39 (s, 3H), 1.58 (m, 2H),0.90 (t, 3H).

Amidine Synthesis 12—N¹-(2-(dimethylamino)ethybbenzamidine (Amidine XI)

Procedure as described for Amidine I using the following amounts: 6.00mL of 2-n-propylaniline (42.6 mmol); 21.3 mL of 2.0 M butyllithium (42.6mmol); 5.00 g of toluonitrile (42.6 mmol). Filtration of the finalpentane solution yielded 9.53 g (89%) of light yellow solid. ¹H NMR (400MHz, CDCl₃): 7.76 (d, 2H), 7.22 (m, 3H), 7.15 (t, 1H), 6.99 (t, 1 H),6.84 (d, 1 H), 4.69 (s, 2H), 2.51 (t, 2H), 2.39 (s, 3H), 1.58 (m, 2H),0.90 (t, 3H).

Amidine Synthesis 13—N¹-(2-(phenylthio)phenyl)benzamidine (Amidine XIII)

Procedure as described for Amidine I using the following amounts andmodifications: 10.06 g of 2-phenylthioaniline (50.0 mmol); 25.0 mL of2.0 M butyllithium (50.0 mmol), 5.20 mL of benzonitrile (51.0 mmol).After refluxing overnight, the solution was green-brown. Addition ofwater yielded a light brown solution with suspended solid. Solution wastaken to dryness, resuspended in 75 mL of pentane, filtered, washed with10 mL of pentane and dried in vacuo yielding 10.56 g (69%) of beigepowder. ¹H NMR (400 MHz, C₆D₆): 7.76 (d, 2H), 7.42 (d, 2H), 7.31 (d,1H), 7.1-6.8 (m, 8 H), 6.78 (t, 1H), 4.08 (s, 2H).

Amidine Synthesis 14—N¹-(2-morpholinoethyl)benzamidine (Amidine XIV)

Procedure as described for Amidine I using the following amounts andmodifications: 6.6 mL of 4-(2-aminoethyl) morpholine (50.0 mmol); 25.0mL of 2.0 M butyllithium (50.0 mmol), 5.20 mL of benzonitrile (51.0mmol). After refluxing overnight, the solution was green-brown. Additionof water yielded a light brown solution with suspended solid. Solutionwas filtered, taken to dryness, resuspended in 100 mL of pentane andstirred vigorously for 1 hour. A white solid deposited, which wasfiltered, washed with 10 mL of pentane and dried in vacuo yielding 8.17g (70%) of white powder. ¹H NMR (400 MHz, CDCl₃): 7.57 (br, 2H), 7.43(m, 3H), 6.4 (br, 1H), 5.3 (br, 1H), 3.71 (m, 4H), 3.47 (br, 2H), 2.65(m, 2H), 2.51 (br, 4H).

Amidine Synthesis 15—N¹ (thiazol-2-vbbenzamidine (Amidine XV)

Procedure as described for Amidine I using the following amounts andmodifications: 5.01 g of 2-aminothiazole (50.0 mmol), 26.0 mL of 2.0 Mbutyllithium (52.0 mmol), 5.20 mL of benzonitrile (51.0 mmol). Afterrefluxing overnight, the solution was green-brown. Addition of wateryielded a red-brown solution with suspended solid. Solution was taken todryness yielding 6.66 g (66%) of yellow-orange material. ¹H NMR (400MHz, C₆D₆): 10.1 (br, 1H), 7.68 (d, 2H), 7.34 (d, 1H), 7.04 (m, 3 H),6.40 (d, 1H), 5.35 (br, 1H), 2.26 (s, 6H).

TABLE 7 Amines, Nitriles, and Product Amidine Compounds of AmidineSyntheses 1-15 Synthesis Designation Amine Nitrile Amidine AmidineSynthesis 1

  Amidine I Amidine Synthesis 2

  Amidine II Amidine Synthesis 3

  Amidine III Amidine Synthesis 4

  Amidine IV Amidine Synthesis 5

  Amidine V Amidine Synthesis 6

  Amidine VI Amidine Synthesis 7

  Amidine VII Amidine Synthesis 8

  Amidine VIII Amidine Synthesis 9

  Amidine IX Amidine Synthesis 10

  Amidine X Amidine Synthesis 11

  Amidine XI Amidine Synthesis 12

  Amidine XII Amidine Synthesis 13

  Amidine XIII Amidine Synthesis 14

  Amidine XIV Amidine Synthesis 15

  Amidine XV

Synthesis of N²-Substituted Amidine Compounds

Acid halides, amines, and phosphorus pentachloride were utilized asobtained from the chemical supplier. The solvents were dried and/orpurified using conventional methods and stored under conditions to limittheir ability to pick-up water. The syntheses of the N²-substitutedamidine compounds were performed using standard air-free procedures andtechniques.

Table 8 provides the acid halides and amines utilized in amide syntheses1 and 2 along with the product amide. Table 8 provides the amides andproduct α-halo-substituted imines of α-halo-substituted imines syntheses1 and 2. Table 9 provides the α-halo-substituted imines and the productN²-substituted amidines of N²-Substituted Amidine Synthesis 1 and 2.

Amide Synthesis 1—N-(2-ethylphenyl)acetamide (Amide I)

2-ethylaniline (12.4 mL, 100 mmol) and NEt₃ (15.4 mL, 110 mmol) wereadded to 100 mL of dichloromethane and cooled to 0° C. Acetyl chloride(7.10 mL 100 mmol) was added dropwise to the cooled aniline solution,affording a peach colored suspension after complete addition. The slurrywas warmed to room temperature and heated to reflux overnight. Thesuspension was taken to dryness and the solid was treated with 200 mL ofwater. The solid was collected by filtration, washed with 200 mL ofdiethylether and dried in vacuo, yielding 9.45 g (58%) of white solid.¹H NMR (400 MHz, CDCl₃): 7.68 (d, 1H), 7.26-7.11 (m, 4H), 2.59 (q, 2H),2.18 (s, 3H), 1.22 (t, 3H).

Amide Synthesis 2—N-(2-tert-butylphenyl)-4-methylbenzamide (Amide II)

2-tert-butylaniline (14.0 mL, 90 mmol) and NEt₃ (14.0 mL, 100 mmol) wereadded to 100 mL of dichloromethane and cooled to 0° C. P-toluoylchloride(12.0 mL, 90 mmol) was added dropwise to the cooled aniline solution,affording a suspension after complete addition. The slurry was warmed toroom temperature and heated to reflux overnight. The suspension wastaken to dryness and the solid was treated with 150 mL of water. Thesolid was collected by filtration, washed with 150 mL of diethyletherand dried in vacuo, yielding 23.14 g (96%) of white solid. ¹H NMR (400MHz, CDCl₃): 7.86 (s, 1H), 7.80 (d, 2H), 7.74 (d, 1H), 7.43 (d, 1H),7.31 (d, 2H), 7.26 (d, 1H), 7.17 (t, 1H), 2.44 (s, 3H), 1.45 (s, 9H).

TABLE 8 Acid Halides, Amines, and Product Amide Compounds of AmideSyntheses 1 and 2. Synthesis Designation Acid Halide Amine Amide AmideSynthesis 1

  Amide I Amide Synthesis 2

  Amide II

α-Halo-Substituted Imine Synthesis1—N-(1-chloroethylidene)-2-ethylbenzenamine (HS Imine I)

Phosphorus pentachloride (8.97 g, 43 mmol) was dissolved in 100 mL ofbenzene. Under a gentle argon purge, N-(2-ethylphenyl)acetamide (AmideI) (6.52 g, 40 mmol) was added slowly with stirring at room temperature.The yellow solution was refluxed for 2 hours. Benzene was removed invacuo, yielding a brown oil. The oil was distilled under reducedpressure (45-50° C., 0.10 Torr) affording 6.08 g (84%) of a clear oil.¹H NMR (400 MHz, C₆D₆): 7.07 (t, 2H), 6.99 (t, 1H), 6.80 (d, 1H), 2.50(q, 2H), 2.08 (s, 3H), 1.11 (t, 3H).

α-Halo-Substituted Imine Synthesis2—2-tert-butyl-N-(chloro(p-tolyl)methylene)benzenamine (HS Imine II)

Phosphorus pentachloride (6.88 g, 33 mmol) was dissolved in 50 mL ofbenzene. Under a gentle argon purge,N-(2-tert-butylphenyl)-4-methylbenzamide (Amide II) (8.02 g, 30 mmol)was added slowly with stirring at room temperature. The yellow solutionwas refluxed for 2 hours. Benzene was removed in vacuo, yielding ayellow solid (8.22 g, 96%). ¹H NMR (400 MHz, C₆D₆): 8.17 (d, 2H), 7.38(d, 1H), 7.11 (t, 1H), 7.06 (t, 1H), 6.90 (d, 2H), 6.85 (d, 1H), 1.98(s, 3H), 1.42 (s, 9H).

TABLE 9 Amides and Product α-Halo-Substituted Imines ofα-Halo-Substituted Imine Syntheses 1-2. Synthesis Designation Amideα-Halo-Substituted Imine α-Halo-Substituted Imine Synthesis 1

  Amide I

  HS Imine I α-Halo-Substituted Imine Synthesis 2

  Amide II

  HS Imine II

N²-Substituted Amidine Synthesis1—N-(2-ethylphenyl)-N²-(2-ethylphenyl)acetamidine (NS Amidine I)

N-(1-chloroethylidene)-2-ethylbenzenamine (HS Imine I) (1.82 g, 10 mmol)was dissolved in 50 mL of toluene. 2-ethylaniline (1.24 mL, 10 mmol) wasadded dropwise at room temperature, resulting in a light pink solution,which was refluxed overnight. Toluene was removed under vacuum. Sodiumhydroxide (100 mL of 0.10 M solution, 10 mmol) was added and thesolution was stirred for 1 hour. The solid that deposited was extractedinto 150 mL of diethylether. The ether layer was dried with MgSO₄,filtered and taken to dryness, leaving 2.20 g of pink solid. The pinksolid was dissolved in 60 mL of pentane and cooled to −30° C. A whitecrystalline solid was collected and dried (2.11 g, 79%). The ¹H NMRspectrum is complex and is consistent with a mixture of E/Z isomers.

N²-Substituted Amidine Synthesis2—N-(2-tert-butylphenyl)-N²-(2-tert-butylphenyl)-4-methylbenzamidine (NSAmidine II)

2-tert-butyl-N-(chloro(p-tolyl)methylene)benzenamine (HS Imine II) (2.86g, 10 mmol) was dissolved in 50 mL of toluene. 2-tert-butylaniline (1.56mL, 10 mmol) was added dropwise at room temperature, resulting in ayellow solution, which was refluxed overnight. Toluene was removed undervacuum. Sodium hydroxide (100 mL of 0.10 M solution, 10 mmol) was addedand the solution was stirred for 1 hour. The solid that deposited wasextracted into 150 mL of diethylether. The ether layer was dried withMgSO₄, filtered, and taken to dryness, leaving 3.72 g (93%) of whitesolid. The ¹H NMR spectrum is complex and is consistent with a mixtureof E/Z isomers.

TABLE 10 α-Halo-Substituted Imines and Product N²-Substituted Amidine ofN²-Substituted Amidine Syntheses 1-2. Synthesis α-Halo-SubstitutedDesignation Imine Amine N²-Substituted Amidine N²-Substituted AmidineSynthesis 1

  HS Imine I

  NS Amidine I N²-Substituted Amidine Synthesis 2

  HS Imine II

  NS Amidine II

Synthesis of Metal Amidinate Compounds

The metal amidinate compound was prepared using the methods describedherein Amines, nitriles, and n-butyl lithium were utilized as obtainedfrom the chemical supplier. The solvents were dried and/or purifiedusing conventional methods and stored under conditions to limit theirability to pick-up water. The syntheses of the amidine compounds wereperformed using standard air-free procedures and techniques.

Metal Amidinate Synthesis 1—LithiumN¹-(2-(diphenylphosphino)ethyl)benzamidinate (NP Amidinate I)

Procedure as described for Amidine I was used with the modification thatthe resultant amidinate was not neutralized. The following amounts wereused with the additional noted modifications: 6.23 g of2-diphenylphosphinoethylamine (27.2 mmol), 13.6 mL of 2.0 M butyllithium(27.2 mmol), 2.80 mL of benzonitrile (27.2 mmol). Normal workup yieldeda thick oil that failed to solidify. The thick oil was dissolved in 100mL of diethylether, cooled to 0° C., and treated with 10.5 mL of 2.0 Mbutyllithium (21.0 mmol). A sticky yellow solid formed upon completeaddition. The diethylether was decanted and replaced with 100 mL ofpentane. Vigorous stirring eventually yielded a free-flowing, off-whitesolid which was collected and dried (7.08 g).

Synthesis of N²-Phosphinylamidine Compounds

The amidine compounds were utilized as prepared using the methodsdescribed herein. The phosphine halides, metal salts, and n-butyllithium were utilized as obtained from the chemical supplier. Thesolvents were dried and/or purified using conventional methods andstored under conditions to limit their ability to pick-up water. Thesyntheses of the N²-phosphinylamidine compounds were performed usingstandard air-free procedures and techniques.

Table 11 provides the amidines and phosphine halides utilized inN²-phosphinylamidine syntheses 1-20 in addition to the productN²-phosphinylamidine compounds.

N²-phosphinylamidine Synthesis1—N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino) benzamidine (NP AmidineI)

N¹-(2,6-dimethylphenyl)benzamidine (3.36 g, 15.0 mmol) was dissolved in50 mL of diethylether and cooled to 0° C. Butyllithium (7.50 mL of 2.0 Msolution in diethylether, 15.0 mmol) was added dropwise, producing afluffy white suspended solid. The slurry was warmed to room temperatureand stirred for 2 hours. Chlorodiphenylphosphine (2.69 mL, 15.0 mmol)was added slowly at room temperature. The suspended solid became finerand denser and the solution became slightly yellow upon completeaddition of the phosphine. Stirring was continued for 1 hour. Thesolution was filtered to remove a small amount of white solid,presumably lithium chloride, and the solvent was removed in vacuo. Theyellow foamy residue was suspended in 50 mL of pentane and stirred for 3hours. Filtration and drying afforded 3.46 g (56%) of off-white solid.

N²-phosphinylamidine Synthesis2—N¹-(2,6-diisopropylphenyl)-N²-(diphenylphosphino) benzamidine (NPAmidine II)

Procedure as described for NP Amidine I using the following amounts:4.20 g N¹-(2,6-diisopropylphenyl)benzamidine (15.0 mmol), 7.50 mL of 2.0M butyllithium (15.0 mmol), 2.70 mL of chlorodiphenylphosphine (15.0mmol). Following removal of lithium chloride via filtration and removalof solvent in vacuo, the sticky residue was dissolved in 20 mL ofpentane, reduced in volume to 5 mL (cold), producing a while solid thatwas filtered and dried (5.33 g, 76%).

N²-phosphinylamidine Synthesis3—N²-(diisopropylphosphino)-4-methyl-N¹-(2,6-dimethylphenyl)-benzamidine(NP Amidine III)

Procedure as described for NP Amidine I using the following amounts:1.19 g of 4-methyl-N¹-(2,6-dimethylphenyl)benzamidine (Amidine III, 5.0mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mLchlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a yellow oil was isolated (1.76g).

N²-phosphinylamidine Synthesis4—4-methyl-N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)-benzamidine(NP Amidine IV)

Procedure as described for NP Amidine I using the following amounts:1.19 g of 4-methyl-N¹-(2,6-dimethylphenyl)benzamidine (Amidine III, 5.0mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.93 mLchlorodiphenylphosphine (5.0 mmol). After filtration to remove lithiumchloride and removal of solvent, the oily product was treated with 20 mLof pentane. After 1 hour stirring at room temperature, a white solidformed. The solution was concentrated to approximately 10 mL andfiltered while cold, yielding 1.64 g (78%) after drying.

N²-phosphinylamidine Synthesis5—4-tert-butyl-N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)-benzamidine(NP Amidine V)

Procedure as described for NP Amidine I using the following amounts:1.40 g of 4-t-butyl-N¹-(2,6-dimethylphenyl)benzamidine (Amidine IV, 5.0mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.93 mLchlorodiphenylphosphine (5.0 mmol). After filtration to remove lithiumchloride and removal of solvent, the sticky residue was treated with 20mL of pentane. After 1 hour stirring at room temperature, the pentanewas removed in vacuo yielding 2.16 g (93%) of off-white solid.

N²-phosphinylamidine Synthesis6—4-tert-butyl-N²-(diisopropylphosphino)-N¹-(2,6-dimethylphenyl)-benzamidine(NP Amidine VI)

Procedure as described for NP Amidine I using the following amounts:1.40 g of 4-t-butyl-N¹-(2,6-dimethylphenyl)benzamidine (Amidine IV, 5.0mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mLchlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a slightly cloudy yellow oilwas isolated (2.04 g, 100%).

N²-phosphinylamidine Synthesis7—N¹-(2-isopropyl-6-methylphenyl)-4-methyl-N²-(diphenyl-phosphino)benzamidine(NP Amidine VII)

Procedure as described for NP Amidine I using the following amounts:1.33 g of N¹-(2-isopropyl-6-methylphenyl)-4-methylbenzamidine (AmidineV, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.93 mLchlorodiphenylphosphine (5.0 mmol). After filtration to remove lithiumchloride and removal of solvent, the residue was treated with 20 mL ofpentane. Prolonged stirring deposited a beige solid which was collectedand dried (1.62 g, 72%).

N²-phosphinylamidine Synthesis8—4-tert-butyl-N¹-(2-tert-butylphenyl)-N²-(diphenylphosphino)-benzamidine(NP Amidine VIII)

Procedure as described for NP Amidine I using the following amounts:1.33 g of N¹-(2-tert-butylphenyl)-4-methylbenzamidine (Amidine VI, 5.0mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.93 mLchlorodiphenylphosphine (5.0 mmol). After filtration to remove lithiumchloride and removal of solvent, the residue was treated with 20 mL ofpentane. Removal of pentane deposited a yellow solid which was collectedand dried (2.05 g, 91%).

N²-phosphinylamidine Synthesis9—N¹-(2-isopropyl-6-methylphenyl)-N²-(diisopropyl-phosphino)-4-methylbenzamidine(NP Amidine IX)

Procedure as described for NP Amidine I using the following amounts:1.33 g of N¹-(2-isopropyl-6-methylphenyl)-4-methylbenzamidine (AmidineV, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mLchlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a yellow semi-solid wasisolated (1.86 g, 97%).

N²-phosphinylamidine Synthesis10—N¹-(2-tert-butylphenyl)-N²-(diisopropylphosphino)-4-methyl-benzamidine(NP Amidine X)

Procedure as described for NP Amidine I using the following amounts:1.33 g of N¹-(2-tert-butylphenyl)-4-methylbenzamidine (Amidine VI, 5.0mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mLchlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a yellow semi-solid wasisolated (1.9 g, 100%).

N²-phosphinylamidine Synthesis11—4-tert-butyl-N¹-(2-tert-butylphenyl)-N²-(diphenylphosphino)-benzamidine(NP Amidine XI)

Procedure as described for NP Amidine I using the following amounts:1.54 g of 4-tert-butyl-N¹-(2-tert-butylphenyl)benzamidine (Amidine VII,5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.93 mLchlorodiphenylphosphine (5.0 mmol). After filtration to remove lithiumchloride and removal of solvent, a yellow solid was collected and dried(2.31 g, 94%).

N²-phosphinylamidine Synthesis12—4-tert-butyl-N¹-(2-tert-butylphenyl)-N²-(diisopropylphosphino)-benzamidine(NP Amidine XII)

Procedure as described for NP Amidine I using the following amounts:1.54 g of 4-tert-butyl-N¹-(2-tert-butylphenyl)benzamidine (Amidine VII,5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mLchlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a yellow semi-solid wasisolated (1.9 g, 100%).

N²-phosphinylamidine Synthesis13—N¹-(2-ethylphenyl)-4-methyl-N²-(diphenylphosphino) benzamidine (NPAmidine XIII)

Procedure as described for NP Amidine I using the following amounts:1.19 g of N¹-(2-ethylphenyl)-4-methylbenzamidine (Amidine VIII, 5.0mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.93 mLchlorodiphenylphosphine (5.0 mmol). After filtration to remove lithiumchloride and removal of solvent, the residue was treated with 20 mL ofpentane. The light yellow solid was collected and dried (1.45 g, 69%).

N²-phosphinylamidine Synthesis14—N¹-(2-ethylphenyl)-N²-(diisopropylphosphino)-4-methyl-benzamidine (NPAmidine XIV)

Procedure as described for NP Amidine I using the following amounts:1.19 g of N¹-(2-ethylphenyl)-4-methylbenzamidine (Amidine VIII, 5.0mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mLchlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a yellow oil was isolated (1.77g, 100%).

N²-phosphinylamidine Synthesis15—4-methyl-N¹-phenyl-N²-diphenylphosphino benzamidine (NP Amidine XV)

Procedure as described for NP Amidine I using the following amounts:1.05 g of 4-methyl-N¹-phenylbenzamidine (Amidine IX, 5.0 mmol), 2.50 mLof 2.0 M butyllithium (5.0 mmol), 0.93 mL chlorodiphenylphosphine (5.0mmol). After filtration to remove lithium chloride and removal ofsolvent, the residue was treated with 20 mL of pentane. The yellow solidwas collected and dried (1.85 g, 94%).

N²-phosphinylamidine Synthesis16—N²-(diisopropylphosphino)-4-methyl-N′-phenylbenzamidine (NP AmidineXVI)

Procedure as described for NP Amidine I using the following amounts:1.05 g of 4-methyl-N¹-phenylbenzamidine (Amidine IX, 5.0 mmol), 2.50 mLof 2.0 M butyllithium (5.0 mmol), 0.80 mL chlorodiisopropylphosphine(5.0 mmol). After filtration to remove lithium chloride and removal ofsolvent, a yellow oil was isolated (1.62 g, 99%).

N²-phosphinylamidine Synthesis17—N¹-(2-isopropylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine(NP Amidine XVII)

N¹-(2-isopropylphenyl)-4-methylbenzamidine (1.26 g, 5.0 mmol) wasdissolved in 25 mL of diethylether and cooled to 0° C. Butyllithium(2.50 mL of 2.0 M solution in pentane, 5.0 mmol) was added dropwise,producing a fluffy white suspended solid. The slurry was warmed to roomtemperature and stirred for 2 hours. Chlorodiisopropylphosphine (0.80mL, 5.0 mmol) was added slowly at room temperature. The suspended solidbecame finer and denser and the solution became slightly yellow uponcomplete addition of the phosphine. Stirring was continued for 1 hour.The solution was filtered to remove a small amount of white solid,presumably lithium chloride, and the solvent was removed in vacuo. Theyellow foamy residue was suspended in 25 mL of pentane, stirred for 2hours and taken to dryness under vacuum, affording 1.64 g (70%) ofyellow solid.

N²-phosphinylamidine Synthesis18—N¹-(2-n-propylphenyl)-N²-(diphenylphosphino)-4-methylbenzamidine (NPAmidine XVIII)

Procedure as described for NP Amidine XVII using the following amounts:1.26 g of N¹-(2-n-propylphenyl)-4-methylbenzamidine (5.0 mmol), 2.50 mLof 2.0 M butyllithium (5.0 mmol), 0.90 mL of chlorodiphenylphosphine(5.0 mmol). 1.76 g (74%) of light yellow solid was collected.

N²-phosphinylamidine Synthesis19—N¹-(2-(dimethylamino)ethyl)-N²-(diisopropylphosphino)-benzamidine (NPAmidine XIX)

Procedure as described for NP Amidine I using the following amounts andmodifications: 0.956 g of N¹-(2-(dimethylamino)ethyl)benzamidine(Amidine XII, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80mL chlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a yellow oil was isolated (1.52g, 99%).

N²-phosphinylamidine Synthesis20—N¹-(2-(dimethylamino)ethyl)-N²-(diphenylphosphino)-benzamidine (NPAmidine XX)

Procedure as described for NP Amidine I using the following amounts andmodifications: 0.956 g of N¹-(2-(dimethylamino)ethyl)benzamidine(Amidine XII, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.93mL chlorodiphenylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, the oily product was treatedwith 20 mL of pentane. After 1 hour stirring at room temperature, awhite solid formed. The solution was concentrated to approximately 10 mLand filtered while cold, yielding 0.891 g (47%) after drying.

N²-phosphinylamidine Synthesis21—N²-(diisopropylphosphino)-N¹-(2-(diphenylphosphino)ethyl)-benzamidine(NP Amidine XXI)

Procedure as described for NP Amidine XVII with the followingmodification: the metal amidinate was not prepared from the amidinecompound but was utilized as isolated in Amidinate Synthesis 1. Theamount of reagents utilized: 1.69 g of lithiumN¹-(2-(diphenylphosphino)ethyl)-benzamidinate (Amidinate 1, 5.0 mmol),0.80 mL chlorodiisopropylphosphine (5.0 mmol). After filtration toremove lithium chloride and removal of solvent, a yellow oil wasisolated (1.72 g, 77%).

N²-phosphinylamidine Synthesis22—N²-(diphenylphosphino)-N¹-(2-(diphenylphosphino)ethyl)-benzamidine(NP Amidine XXII)

Procedure as described for NP Amidine XVII with the followingmodification: the metal amidinate was not prepared from the amidinecompound but was utilized as isolated in Amidinate Synthesis 1. Theamount of reagents utilized: 1.69 g of lithiumN¹-(2-(diphenylphosphino)ethyl)-benzamidinate (Amidinate 1, 5.0 mmol),0.93 mL chlorodiphenylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, the yellow foamy residue wastreated with 40 mL of pentane. Scraping the walls of the flask yielded ayellow solid that was collected and dried (2.04 g, 79%).

N²-phosphinylamidine Synthesis23—N²-(diisopropylphosphino)-N¹-(2-(phenylthio)phenyl)-benzamidine (NPAmidine XXIII)

Procedure as described for NP Amidine I using the following amounts andmodifications: 1.52 g of N¹-(2-(phenylthio)phenyl)benzamidine (AmidineXIV, 5.0 mmol), 2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mLchlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a yellow oil was isolated (2.07g, 98%).

N²-phosphinylamidine Synthesis24—N²-(diphenylphosphino)-N¹-(2-(phenylthio)phenyl)benzamidine (NPAmidine XXIV)

Procedure as described for NP Amidine I using the following amounts andmodifications: 1.34 g of N¹-(2-(phenylthio)phenyl)benzamidine (AmidineXIV, 4.4 mmol), 2.20 mL of 2.0 M butyllithium (4.4 mmol), 0.78 mLchlorodiphenylphosphine (4.4 mmol). After filtration to remove lithiumchloride and removal of solvent, a sticky solid was isolated (2.01 g,93%).

N²-phosphinylamidine Synthesis25—N²-(diisopropylphosphino)-N¹-(2-morpholinoethyl)benzamidine (NPAmidine XXV)

Procedure as described for NP Amidine XVII using the following amounts:0.956 g of N¹-(2-morpholinoethyl)benzamidine (Amidine XV, 5.0 mmol),2.50 mL of 2.0 M butyllithium (5.0 mmol), 0.80 mLchlorodiisopropylphosphine (5.0 mmol). After filtration to removelithium chloride and removal of solvent, a yellow oil was isolated (1.71g, 98%).

N²-phosphinylamidine Synthesis26—N¹-(2-morpholinoethyl)-N²-(diphenylphosphino)benzamidine (NP AmidineXXVI)

Procedure as described for NP Amidine XVII using the following amounts:1.17 g of N¹-(2-morpholinoethyl)benzamidine (Amidine XV, 5.0 mmol), 2.50mL of 2.0 M butyllithium (5.0 mmol), 0.93 mL chlorodiphenylphosphine(5.0 mmol). After filtration to remove lithium chloride and removal ofsolvent, the oily product was treated with 20 mL of pentane. Removal ofthe pentane yielded 1.33 g of off-white solid (64%).

N²-phosphinylamidine Synthesis27—N²-(diphenylphosphino)-N¹-(thiazol-2-yl)benzamidine (NP AmidineXXVII)

Procedure as described for NP Amidine XVII using the following amounts:3.06 g of N¹-(thiazol-2-yl)benzamidine (Amidine XVI, 15.0 mmol), 7.50 mLof 2.0 M butyllithium (15.0 mmol), 0.93 mL of chlorodiphenylphosphine(15.0 mmol). Following removal of lithium chloride, the solvent wasremoved from the filtrate to give a sticky residue. The sticky residuewas suspended in 100 mL of pentane. Vigorous stirring and scrapingeventually yielded an off-white solid after 2 hours. The solid wascollected and dried (2.59 g). The lithium chloride solid separated fromreaction solution was extracted with 100 mL of diethylether, filtered,taken to dryness, and treated with 100 mL of pentane. Stirring andscraping produced white solid that was collected and dried yielding anadditional 1.56 g of solid. Combined yield 4.15 g (71%).

N²-phosphinylamidine Synthesis28—N¹-(2-ethylphenyl)-N-(2-ethylphenyl)—N-(diisopropylphosphino)acetamidine(NSP Amidine I)

N¹-(2-ethylphenyl)-N-(2-ethylphenyl)acetamidine (NS Amidine I) (0.798 g,3.0 mmol) was dissolved in 50 mL of diethylether and cooled to 0° C.Butyllithium (1.50 mL of 2.0 M solution in pentane, 3.0 mmol) was addeddropwise, producing a light yellow solution. The solution was warmed toroom temperature and stirred for 2 hours. Chlorodiisopropylphosphine(0.48 mL, 3.0 mmol) was added slowly at room temperature. A whitesuspension formed, which was stirred overnight at room temperature. Theslurry was filtered to remove a small amount of white solid, presumablylithium chloride, and the solvent was removed in vacuo to produce 1.14 g(99%) of yellow oil.

N²-phosphinylamidine Synthesis29—N¹-(2-tert-butylphenyl)-N-(2-tert-butylphenyl)-N-(diisopropylphosphino)-4-methylbenzamidine(NSP Amidine II)

N¹-(2-tert-butylphenyl)-N-(2-tert-butylphenyl)-4-methylbenzamidine (NSAmidine II) (1.20 g, 3.0 mmol) was dissolved in 50 mL of diethyletherand cooled to 0° C. Butyllithium (1.50 mL of 2.0 M solution in pentane,3.0 mmol) was added dropwise, producing a light yellow solution. Thesolution was warmed to room temperature and stirred for 2 hours.Chlorodiisopropylphosphine (0.48 mL, 3.0 mmol) was added slowly at roomtemperature. A white suspension formed, which was stirred overnight atroom temperature. The slurry was filtered to remove a small amount ofwhite solid, presumably lithium chloride, and the solvent was removed invacuo to produce 1.35 g (87%) of yellow solid.

TABLE 11 Amidines, Phosphine Halides, and Product N²-Phosphinyl AmidineCompounds of N²-Phosphinyl Amine Syntheses 1-29. Phosphine Halide Run #Amidine Compound N²-Phosphinyl Amidine N²-Phosphinyl- amidine Synthesis 1

N²-Phosphinyl- amidine Synthesis  2

N²-Phosphinyl- amidine Synthesis  3

N²-Phosphinyl- amidine Synthesis  4

N²-Phosphinyl- amidine Synthesis  5

N²-Phosphinyl- amidine Synthesis  6

N²-Phosphinyl- amidine Synthesis  7

N²-Phosphinyl- amidine Synthesis  8

N²-Phosphinyl- amidine Synthesis  9

N²-Phosphinyl- amidine Synthesis 10

N²-Phosphinyl- amidine Synthesis 11

N²-Phosphinyl- amidine Synthesis 12

N²-Phosphinyl- amidine Synthesis 13

N²-Phosphinyl- amidine Synthesis 14

N²-Phosphinyl- amidine Synthesis 15

N²-Phosphinyl- amidine Synthesis 16

N²-Phosphinyl- amidine Synthesis 17

N²-Phosphinyl- amidine Synthesis 18

N²-Phosphinyl- amidine Synthesis 19

N²-Phosphinyl- amidine Synthesis 20

N²-Phosphinyl- amidine Synthesis 21

N²-Phosphinyl- amidine Synthesis 22

N²-Phosphinyl- amidine Synthesis 23

N²-Phosphinyl- amidine Synthesis 24

N²-Phosphinyl- amidine Synthesis 25

N²-Phosphinyl- amidine Synthesis 26

N²-Phosphinyl- amidine Synthesis 27

N²-Phosphinyl- amidine Synthesis 28

N²-Phosphinyl- amidine Synthesis 29

Synthesis of N²-Phosphinylamidine Compounds

The N²-phosphinylamidine compounds were utilized as prepared using themethods described herein. The halogenated compounds and butyllithiumwere utilized as obtained from the chemical supplier. The solvents weredried and/or purified using conventional methods and stored underconditions to limit their ability to pick-up water. The syntheses of thealkylated N²-phosphinylamidine compounds were performed using standardair-free procedures and techniques.

Table 12 provides the amidine compounds and halogenated compoundsutilized in the N²-phosphinylamidine alkylations 1 and 2 in addition tothe product alkylated N²-phosphinylamidine compounds.

N²-phosphinylamidine Alkylation1—N¹-(2-isopropylphenyl)-N-(diisopropylphosphino)-N-methyl-4-methylbenzamidine(NSP Amidine III)

N¹-(2-isopropylphenyl)-N-(diisopropylphosphino)-4-methylbenzamidine(1.40 g, 3.0 mmol) was dissolved in 25 mL of diethylether and cooled to0° C. Butyllithium (1.50 mL of 2.0 M solution in pentane, 3.0 mmol) wasadded dropwise, producing a cloudy yellow suspension. The slurry waswarmed to room temperature and stirred for 2 hours. Methyliodide (1.5 mLof 2.0 M solution in THF) was added dropwise at room temperature andstirred continued for 1 hour. The solution became clear yellow. Thesolvent was removed under vacuum and replaced with 20 mL ofdiethylether. A small amount of solid (presumably LiI) was removed byfiltration and the filtrate was taken to dryness, yielding 0.94 g (65%)of sticky yellow solid.

N²-phosphinylamidine Alkylation2—N¹-(2-n-propylphenyl)-N-(diphenylphosphino)-N-methyl-4-methylbenzamidine(NSP Amidine IV)

Procedure as described for NSP Amidine III using the following amounts:1.42 g ofN¹-(2-n-propylphenyl)-N-(diphenylphosphino)-4-methylbenzamidine (3.0mmol), 1.50 mL of 2.0 M butyllithium (15.0 mmol), 1.50 mL of 2.0 Mmethyliodide (3.0 mmol). Following removal of lithium iodide viafiltration and removal of solvent in vacuo, a yellow sticky residue wasrecovered (1.63 g, 67%).

TABLE 12 Amidine Compounds, Halogenated Compounds, and ProductN²-Phosphinylamidine Compounds of N²-Phosphinylamidine Alkylations 1 and2. N²-Phosphinyl Halogenated Alkylated N²-Phosphinyl Run AmidineCompound Amidine N²-Phosphinyl- amidine Alkylation 1

CH₃I

N²-Phosphinyl- amidine Alkylation 2

CH₃I

Synthesis of N²-Phosphinylamidinate Metal Salts

The N²-phosphinylamidinecompounds were utilized as prepared using themethods described herein. The metal salts and butyllithium were utilizedas obtained from the chemical supplier. The solvents were dried and/orpurified using conventional methods and stored under conditions to limittheir ability to pick-up water. The syntheses of theN²-phosphinylamidinate metal salt complexes were performed usingstandard Schlenk and/or inert atmosphere glove box techniques. It shouldbe noted that the Tables in this section provide what is believed to bethe structure of a freshly prepared N²-phosphinylamidinate metal saltcomplex based upon the structure of an N²-phosphinylamidine metalcomplex subjected to X-ray crystallography. However, theN²-phosphinylamidinate metal salt complex can contain more or or lessneutral ligand than is shown in the structure without departing from thepresent disclosure. As will be come apparent, and without being limitedto theory, it is believed that the structure of theN²-phosphinylamidinate metal salt complex can change with time and thatthis change can be due to the loss of the neutral ligand from theN²-phosphinylamidinate metal complex or N²-phosphinylamidinate metalcomplex crystal lattice. Additionally, the N²-phosphinylamidinate metalcomplex structures formally show a monomeric form of a metal compoundcomplexed to N²-phosphinylamidinate. However, it should be noted thatthese structures do not necessarily imply that dimeric and/or oligomericforms of structures having bridging X_(p) groups (e.g. Cl) which connectmetal atoms complexed to the N²-phosphinylamidinate are not formed. Themonomeric structures provided herein can encompass the dimeric and/oroligomeric forms of structures having bridging X_(p) groups which canconnect metal atoms complexed to the N²-phosphinylamidinate.

Table 13 provides the N²-phosphinylamidine compounds and metal saltscompounds utilized in the N²-phosphinylamidinate metal salt synthesis1-3 in addition to the product N²-phosphinylamidinate metal saltcomplexes.

N²-Phosphinylamidinate Metal Salt Synthesis1—[N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)benzamidinate](THF)CrCl₂(NP Amidine Metal Salt Complex A1)

N¹-(2,6-dimethylphenyl)-N-(diphenylphosphino)benzamidine (NP Amidine I)(0.204 g, 0.500 mmol) was dissolved in 20 mL of THF and cooled to −100°C. Butyllithium (0.25 mL of 2.0 M solution in diethyl ether, 0.50 mmol)was added dropwise, resulting in a yellow solution upon warming to roomtemperature. Stirring continued for 2 hours. CrCl₃(THF)₃ (0.187 g, 0.500mmol) was dissolved in 10 mL of THF and was added dropwise to theamidinate solution. The solution was dark green after complete addition.Stirring was continued for 1 hour at room temperature after which thesolvent was removed in vacuo. Diethyl ether (30 mL) was added and thesolution was filtered to remove a white precipitate, presumably LiCl.The green filtrate was taken to dryness yielding 0.250 g of green solid.Anal. Calc. (Found) for C₃₁H₃₂ON₂PCrCl₂: C, 61.80 (56.91); H, 5.35(5.37); N, 4.65 (4.79).

N²-Phosphinylamidinate Metal Salt Synthesis2—[N¹-(2,6-diisopropylphenyl)-N²-(diphenylphosphino)benzamidinate](THF)CrCl, (NP Amidine Metal Salt Complex A2)

N¹-(2,6-diisopropylphenyl)-N-(diphenylphosphino)benzamidine (NP AmidineII, 0.464 g, 1.00 mmol) was dissolved in 50 mL of diethyl ether andcooled to 0° C. Butyllithium (0.50 mL of 2.0 M solution in diethylether, 1.00 mmol) was added dropwise, resulting in a yellow solutionafter complete addition. The mixture was warmed to room temperature andstirred for 1 hour. CrCl₃(THF)₃ (0.374 g, 1.00 mmol) was dissolved in 20mL of THF and treated with small portions of the benzamidinate solutionvia pipet. The resulting green solution was stirred for 2 hours at roomtemperature. The mixture was taken to dryness, extracted into 50 mL ofdiethyl ether, filtered to remove LiCl, and taken to dryness to yield agreen powder (0.627 g, 95.2%). Anal. Calc. (Found) for C₃₅H₄OON2PCrC12:C, 63.83 ( ); H, 6.12 ( ); N, 4.25 ( ).

N²-Phosphinylamidinate Metal Salt Synthesis3—[4-methyl-N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)benzamidinate](THF)CrCl, (NP Amidine Metal Salt Complex A3)

4-methyl-N¹-(2,6-dimethylphenyl)-N-(diphenylphosphino)benzamidine (NPAmidine IV, 0.211 g, 0.500 mmol) was dissolved in 50 mL of diethyl etherand cooled to 0° C. Butyllithium (0.25 mL of 2.0 M solution in diethylether, 0.50 mmol) was added dropwise, resulting in a yellow solutionafter complete addition. The mixture was warmed to room temperature andstirred for 1 hour. CrCl₃(THF)₃ (0.187 g, 0.500 mmol) was dissolved in20 mL of THF and treated with small portions of the benzamidinatesolution via pipet. The resulting green solution was stirred for 2 hoursat room temperature. The mixture was taken to dryness, extracted into 15mL of diethyl ether, filtered to remove LiCl, and taken to dryness,affording 0.155 g of solid (54.5%). Anal. Calc. (Found) forC₃₂H₃₄ON₂PCrCl₂: C, 67.61 ( ); H, 6.03 ( ); N, 4.93 ( ).

TABLE 13 N²-Phosphinylamidine Compounds, Metal Salts, and ProductN²-Phosphinylamidinate Metal Salt Complexes of N²-PhosphinylamidinateMetal Salt Syntheses 1-3. Metal Salt Run # N²-Phosphinyl Amidine MetalSalt N²-Phosphinyl Amidinate N²-Phosphinyl- amidinate Metal SaltSynthesis 3

CrCl₃(THF)₃

N²-Phosphinyl- amidinate Metal Salt Synthesis 3

CrCl₃(THF)₃

N²-Phosphinyl- amidinate Metal Salt Synthesis 3

CrCl₃(THF)₃

Synthesis of N²-Substituted Amidine Compounds

Amines, nitriles, n-butyl lithium, phosphine halides were utilized asobtained from the chemical supplier. The solvents were dried and/orpurified using conventional methods and stored under conditions to limittheir ability to pick-up water. The syntheses of the amidine compoundswere performed using standard air-free procedures and techniques.Several N²-phosphinylamidine compounds were prepared from amines,nitriles, n-butyl lithium, phosphine halides without isolating theintermediate metal amidinate of amidine compound. The procedure utilizedis provided below.

A glass 500 mL three-necked round bottomed flask fitted with a) anadapter that can connect to two glass addition funnels, b) a nitrogenpurge line, and c) vacuum source. The flask also contained a magneticstir bar to enable stirring with a magnetic stirrer. The round bottomedflask apparatus was then purged with dry nitrogen for 30 minutes beforeuse while the round bottomed flask was cooled in an ice water bath.

In a dry box, seven addition funnels were prepared. The first additionfunnel (125 mL) was charged with 110 mL anhydrous diethyl ether. Thesecond addition funnel (125 mL) was charged with 90 mL anhydrous diethylether and the amine. The third addition funnel (50 mL) was charged with2.0 M n-butyl lithium in pentane. The fourth addition funnel (125 ml)was charged with a nitrile. A fifth addition funnel (500 mL) was chargedwith about 210 mL of anhydrous THF. A sixth addition funnel (125 mL) wascharged with a chlorophosphine. The seventh addition funnel (250 mL) wascharged with 225 mL of anhydrous n-pentane. The addition funnelsprepared, sealed, and removed from the dry box as needed.

The amine solution and diethyl ether addition funnels were mounted tothe round bottomed flask adapter. Once the apparatus had been purged andthe round bottomed flask cooled, all of the amine solution was chargedto the round bottomed flask. Then 45 mL of diethyl ether from thediethyl ether addition funnel was sent through the round bottomed flaskadapter to flush the amine into the round bottomed flask. The aminesolution addition funnel was replaced with the n-butyl lithium additionfunnel. When the contents of the round bottomed flask attained atemperature between 0° C. and 5° C., all of the n-butyl lithium solutionwas added dropwise to the round bottomed flask over about 20 minutes.The ice water bath was removed from around the round bottomed flask andthe contents of the round bottomed flask mixture were allowed to slowlywarm to room temperature. The third addition funnel was replaced withthe nitrile addition funnel while the contents of the round bottomedflask were stirred for two hours at room temperature. The nitrile wasthen added dropwise to the round bottomed flask over about 20 minutes.The contents of the round bottomed flask were then stirred at roomtemperature for one hour.

Using reduced pressure, the ether was removed from the round bottomedflask leaving a yellow-brown solid. The round bottomed flask was purgedwith dry nitrogen. The fourth addition funnel was replaced with the THFaddition funnel Once the round bottomed flask had been purged withnitrogen, all of the THF was added to the round bottomed flask. Thecontents of the round bottomed flask were heated to 60° C. and stirredfor about 16 hours. The contents of the round bottomed flask were cooledto room temperature. While the contents of the round bottomed flask werecooling to room temperature the fifth addition funnel was replaced withthe addition funnel containing the chlorophosphine. Once the contents ofthe round bottomed flask attained room temperature, all of thechlorophosphine was added dropwise to the round bottomed flask overabout 20 minutes and then stirred for one hour at room temperature. TheTHF was then evaporated the THF from the round bottomed flask underreduced pressure while applying heat with a heating mantle to main atemperature around 50° C. to 60° C. The sixth addition funnel wasreplaced with the addition funnel containing n-pentane. The roundbottomed flask was allowed to cool to room temperature and about 100 mlof n-pentane was added to the round bottomed flask to disperse the solidresidue to give a brown solution which was stirred for about three hoursat room temperature to dissolve the organic product. The finely dividedLiCl salt was then removed from the solution by suction filtration. TheN²-phosphinylamidine compound was then collected by crystallization fromthe clear brown filtrate solution. Typical yield range from 60% to 80%.

Five different syntheses were performed using this procedure. Thematerials utilized and the quantity of the reagent is provided in Table14.

TABLE 14 Regents utilized to prepare N²-phosphinylamidine compoundsusing amines, nitriles, n-butyl lithium, phosphine halides withoutisolating the intermediate metal amidinate of amidine compound. RunAmine n-Butyl Lithiium Nitrile Chlorophosphine 1 2,4,6-Trimethyl- 35.5mL - 71 mmol 4-t-Butyl- Diisopropyl- aniline benzonitrile phosphorusChloride (9.2 g - 68 mmol) (11 g - 69 mmol) (27.9 g - 68 mmol) 22,4,6-Trimethyl- 35.5 mL - 71 mmol 3,5-dimethyl- Diisopropyl- aniline4-methoxy- phosphorus Chloride (9.2 g - 68 mmol) benzonitrile   (27 g -68 mmol) (11.2 g - 69 mmol)   3 2,4,6-Trimethyl- 35.5 mL - 71 mmol4-t-Butyl- Diphenyl- aniline benzonitrile phosphorus Chloride (9.2 g -68 mmol) (11 g - 69 mmol) (32.5 g - 68 mmol) 4 2,4,6-Trimethyl- 35.5mL - 71 mmol Benzonitrile Diisopropyl- aniline (11.2 g - 69 mmol)  phosphorus Chloride (9.2 g - 68 mmol) (32.6 g - 68 mmol) 52,4,6-Trimethyl- 35.5 mL - 71 mmol 4-t-Butyl- Diisobutyl- anilinebenzonitrile phosphorus Chloride (9.2 g - 68 mmol) (11 g - 69 mmol)(32.5 g - 68 mmol)

Synthesis of N²-Phosphinylamidine Metal Salt Complexes

The N²-phosphinylamidine compounds were utilized as prepared using themethods described herein. The metal salts and butyllithium were utilizedas obtained from the chemical supplier. The solvents were dried and/orpurified using conventional methods and stored under conditions to limittheir ability to pick-up water. The syntheses of theN²-phosphinylamidine metal salt complexes were performed using standardSchlenk and/or inert atmosphere glove box techniques. It should be notedthat the Tables in this section provide what is believed to be thestructure of a freshly prepared N²-phosphinylamidine metal salt complexbased upon the structure of an N²-phosphinylamidine metal complexsubjected to X-ray crystallography. However, the N²-phosphinylamidinemetal salt complex can contain more or or less neutral ligand than isshown in the structure without departing from the present disclosure. Aswill be come apparent, and without being limited to theory, it isbelieved that the structure of the N²-phosphinylamidine metal saltcomplex can change with time and that this change can be due to the lossof the neutral ligand from the N²-phosphinylamidine metal complex orN²-phosphinylamidine metal complex crystal lattice. It should also benoted that the structure of the N²-phosphinylamidine metal saltcomplexes utilizing an N²-phosphinylamidine compound including a metalsalt complexing group shows that the metal complexing group is notligated to the metal salt. It is not known whether or not the metalcomplex is ligated to the metal salt and the present disclosureencompasses the possibility that the metal salt complexing group isligated or not ligated to the metal salt any particularN²-phosphinylamidine metal salt complex. Additionally, theN²-phosphinylamidine metal complex structures formally show a monomericform of a metal compound complexed to a N²-phosphinylamidine compound.However, it should be noted that these structures do not necessarilyimply that dimeric and/or oligomeric forms of structures having bridgingX_(p) groups (e.g. Cl) which connect metal atoms complexed to theN²-phosphinylamidine compound are not formed. The monomeric structuresprovided herein can encompass the dimeric and/or oligomeric forms ofstructures having bridging X_(p) groups which can connect metal atomscomplexed to the N²-phosphinylamidine compound.

Table 15 provides the N²-phosphinylamidine compounds and metal saltscompounds utilized in the N²-phosphinylamidine metal salt synthesis 1-19in addition to the product N²-phosphinylamidine metal salt complexes.

N²-Phosphinylamidine Metal Salt Complex Synthesis1—[N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B1)

CrCl₃(THF)₃ (0.200 g, 0.534 mmol) was dissolved in 15 mL of THF.N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)benzamidine (NP Amidine I)(0.220 g, 0.534 mmol) was added as a solid in small portions. Theresulting blue-green solution was stirred overnight at room temperatureand taken to dryness. The residue was washed with 10 mL of diethyl etherand 20 mL of pentane, collected and dried affording 0.317 g (83.5%) ofblue solid, which analyzed satisfactorily as a THF solvate. Anal. Calc.(Found) for C₃₅H₄₁O₂N₂PCrCl₃: C, 59.12 (58.57); H, 5.81 (5.84); N, 3.94(3.92)

N²-Phosphinylamidine Metal Salt Complex Synthesis2—[4-methyl-N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B2)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts:4-methyl-N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)benzamidine (NPAmidine IV, 0.211 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol). Theresulting blue-green solution was stirred overnight at room temperature,taken to dryness, washed with 10 mL of pentane and dried to yield 0.313g of green product (95.7%). Anal. Calc. (Found) for C₃₂H₃₅ON₂PCrCl₃: C,58.86 ( ); H, 5.40 ( ); N, 4.29 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis3—[N²-(diisopropylphosphino)-4-methyl-N¹-(2,6-dimethylphenyl)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B3)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts:N²-(diisopropylphosphino)-4-methyl-N¹-(2,6-dimethylphenyl)benzamidine(NP Amidine III, 0.158 g, 0.464 mmol), CrCl₃(THF)₃ (0.174 g, 0.464mmol). The resulting blue-green solution was stirred overnight at roomtemperature and taken to dryness. The residue was dissolved in 3 mL ofTHF and recrystallized via pentane diffusion to yield 0.186 g (68.5%) ofcrystalline blue solid. Anal. Calc. (Found) for C₂₆H₃₉ON₂PCrCl₃: C,53.39 ( ); H, 6.72 ( ); N, 4.79 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis4—[4-tert-butyl-N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B4)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts:4-tert-butyl-N¹-(2,6-dimethylphenyl)-N²-(diphenylphosphino)benzamidine(NP Amidine V, 0.232 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol).The resulting blue solution was stirred for 2 hours at room temperature,depositing a light blue solid. The volatiles were removed in vacuo, theresidue was washed with pentane and dried affording 0.348 g (99%) ofblue solid. Anal. Calc. (Found) for C₃₅H₄₁ON₂PCrCl₃: C, 60.48 ( ); H,5.95 ( ); N, 4.03 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis5—[4-tert-butyl-N²-(diisopropylphosphino)-N¹-(2,6-dimethylphenyl)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B5)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts, with the following modifications:4-tert-butyl-N²-(diisopropylphosphino)-N¹-(2,6-dimethylphenyl)benzamidine(NP Amidine VI, 0.256 g, 0.644 mmol), CrCl₃(THF)₃ (0.241 g, 0.644 mmol).The ligand was preweighed in a disposable pipet and washed into a vialwith 10 mL of diethyl ether. The ligand solution was added dropwise toCrCl₃(THF)₃ dissolved in 15 mL of THF. The resulting blue solution wasstirred for 1 hour at room temperature, depositing a light blue solid.After the volatiles were removed in vacuo, the residue was washed withpentane and dried affording 0.403 g (99%) of blue solid. Anal. Calc.(Found) for C₂₉H₄₅ON₂PCrCl₃: C, 55.55 ( ); H, 7.23 ( ); N, 4.47 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis6—[N¹-(2-isopropyl-6-methylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B6)

Procedure as described for NP Amidine Metal Salt Complex B5 using thefollowing amounts:N¹-(2-isopropyl-6-methylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine(NP Amidine IX, 0.192 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol).The resulting blue solution was stirred for 1 hour at room temperature.After the volatiles were removed in vacuo, the residue was washed withpentane and dried affording 0.303 g (99%) of blue solid. Anal. Calc.(Found) for C₂₈H₄₃ON₂PCrCl₃: C, 54.86 ( ); H, 7.07 ( ); N, 4.57 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis7—N¹-(2-tert-butylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B7)

Procedure as described for NP Amidine Metal Salt Complex B5 using thefollowing amounts:N¹-(2-tert-butylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine(NP Amidine X, 0.192 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol).The resulting green solution was stirred for 1 hour at room temperature.After the volatiles were removed in vacuo, the residue was washed withpentane and dried affording 0.305 g (99%) of blue solid. Anal. Calc.(Found) for C₂₈H₄₃ON₂PCrCl₃: C, 54.86 ( ); H, 7.07 ( ); N, 4.57 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis8—[4-tert-butyl-N¹-(2-tert-butylphenyl)-N²-(diphenylphosphino)benzamidine](THF)CrCl,(NP Amidine Metal Salt Complex B8)

4-tert-butyl-N¹-(2-tert-butylphenyl)-N²-(diphenylphosphino)benzamidine(NP Amidine XI) (0.212 g, 0.430 mmol) was dissolved in 20 mL of THF.Solid CrCl₂ (0.0615 g, 0.500 mmol) was added to the amidine solution.The solution slowly became lime green. Stirring was continued overnightat room temperature, after which the solvent was removed in vacuo. Thegreen residue was washed with pentane and taken to dryness yielding0.160 g of green solid.

N²-Phosphinylamidine Metal Salt Complex Synthesis9—[4-tert-butyl-N¹-(2-tert-butylphenyl)-N²-(diisopropylphosphino)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B9)

Procedure as described for NP Amidine Metal Salt Complex B5 using thefollowing amounts:4-tert-butylN¹-(2-tert-butylphenyl)-N²-(diisopropylphosphino)benzamidine(NP Amidine XII, 0.212 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500mmol). The resulting green solution was stirred overnight at roomtemperature. After the volatiles were removed in vacuo, the residue waswashed with pentane and dried affording 0.253 g (77.2%) of green solid.Anal. Calc. (Found) for C₃₁H₄₉ON₂PCrCl₃: C, 56.84 ( ); H, 7.54 ( ); N,4.28 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis10—[N¹-(2-ethylphenyl)-4-methyl-N²-(diphenylphosphino)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B10)

Procedure as described for NP Amidine Metal Salt Complex B5 using thefollowing amounts:N¹-(2-ethylphenyl)-4-methyl-N²-(diphenylphosphino)benzamidine (NPAmidine XIII, 0.211 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol).The resulting blue solution was stirred overnight at room temperature.After the volatiles were removed in vacuo, the residue was washed withpentane and dried affording 0.357 g (%) of blue solid. Anal. Calc.(Found) for C₃₂H₃₅ON₂PCrCl₃: C, 58.86 ( ); H, 5.40 ( ); N, 4.29 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis11—[N¹-(2-ethylphenyl)—N²-(diisopropylphosphino)-4-methylbenzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B11)

Procedure as described for NP Amidine Metal Salt Complex B5 using thefollowing amounts:N¹-(2-ethylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine (NPAmidine XIV, 0.177 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol).The resulting blue solution was stirred overnight at room temperature.After the volatiles were removed in vacuo, the residue was washed withpentane and dried affording 0.281 g (96%) of blue solid. Anal. Calc.(Found) for C₂₆H₃₉ON₂PCrCl₃: C, 53.38 ( ); H, 6.72 ( ); N, 4.79 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis12—[4-methyl-N¹-phenyl-N²-(diphenylphosphino)benzamidine](THF)CrCl₃ (NPAmidine Metal Salt Complex B12)

Procedure as described for NP Amidine Metal Salt Complex B5 using thefollowing amounts: 4-methyl-N¹-phenyl-N²-(diphenylphosphino)benzamidine(NP Amidine XV, 0.197 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol).The resulting blue solution was stirred overnight at room temperature.After the volatiles were removed in vacuo, the residue was washed withpentane and dried affording 0.327 g (%) of turquoise solid. Anal. Calc.(Found) for C₃₀H₃₁ON₂PCrCl₃: C, 57.66 ( ); H, 5.00 ( ); N, 4.48 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis13—[N²-(diisopropylphosphino)-4-methyl-N¹-phenylbenzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B13)

Procedure as described for NP Amidine Metal Salt Complex B5 using thefollowing amounts:N²-(diisopropylphosphino)-4-methyl-N¹-phenylbenzamidine (NP Amidine XVI,0.163 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol). The resultingblue solution was stirred overnight at room temperature. After thevolatiles were removed in vacuo, the residue was washed with pentane anddried affording 0.278 g (99%) of blue solid. Anal. Calc. (Found) forC₂₄H₃₅ON₂PCrCl₃: C, 51.76 ( ); H, 6.34 ( ); N, 5.03 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis14—[N¹-(2-isopropylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B14)

N¹-(2-isopropylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine (NPAmidine XVII, 0.234 g, 0.637 mmol) was dissolved in 10 mL of THF andadded dropwise to a solution of CrCl₃(THF)₃ (0.193 g, 0.515 mmol)dissolved in 15 mL of THF. The resulting dark blue solution was stirredovernight at room temperature and taken to dryness. The residue waswashed with 20 mL of pentane, collected and dried affording 0.336 g ofblue solid.

N²-Phosphinylamidine Metal Salt Complex Synthesis15—[N¹-(2-n-propylphenyl)-N²-(diphenylphosphino)-4-methylbenzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex B15)

N¹-(2-n-propylphenyl)-N²-(diphenylphosphino)-4-methylbenzamidine (NPAmidine XVIII, 0.236 g, 0.541 mmol) was dissolved in 10 mL of THF andadded dropwise to a solution of CrCl₃(THF)₃ (0.190 g, 0.507 mmol)dissolved in 15 mL of THF. The resulting dark blue solution was stirredovernight at room temperature and taken to dryness. The residue waswashed with 20 mL of pentane, collected and dried affording 0.379 g ofblue solid.

N²-Phosphinylamidine Metal Salt Complex Synthesis16—[N¹-(2-ethylphenyl)—N²-(2-ethylphenyl)—N²-(diisopropylphosphino)acetamidine](THF)CrCl₃(NP Amidine Metal Salt Complex C1)

N¹-(2-ethylphenyl)-N²-(2-ethylphenyl)-N²-(diisopropylphosphino)acetamidine(NPS Amidine I, 0.191 g, 0.500 mmol) was dissolved in 15 mL of THF.CrCl₃(THF)₃ (0.187 g, 0.500 mmol) was added as a solid in smallportions. The resulting blue solution was stirred overnight at roomtemperature and taken to dryness. The residue was washed with 20 mL ofpentane, collected and dried affording 0.256 g (81%) of blue solid.

N²-Phosphinylamidine Metal Salt Complex Synthesis17—[N¹-(2-tert-butylphenyl)-N²-(2-tert-butylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine](THF)CrCl₃ (NP Amidine Metal Salt Complex C2)

N¹-(2-tert-butylphenyl)-N²-(2-tert-butylphenyl)-N²-(diisopropylphosphino)-4-methylbenzamidine(NPS Amidine II, 0.261 g, 0.50 mmol) was added to CrCl₃ (0.064 g, 0.50mmol) suspended in 15 mL of THF. The solution, which slowly becamegreen, was stirred overnight at room temperature and taken to dryness.The residue was washed with 20 mL of pentane, collected and driedaffording 0.120 g of green solid.

N²-Phosphinylamidine Metal Salt Complex Synthesis18—[N¹-(2-isopropylphenyl)-N¹-(diisopropylphosphino)-N²-methyl-4-methylbenzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex C3)

CrCl₃(THF)₃ (0.187 g, 0.500 mmol) was dissolved in 15 mL of THF.N¹-(2-isopropylphenyl)-N²-(diisopropylphosphino)-N²-methyl-4-methylbenzamidine(NSP Amidine III, 0.241 g, 0.500 mmol) was added as a solid in smallportions. The resulting blue-green solution was stirred overnight atroom temperature and taken to dryness. The residue was washed with 20 mLof pentane, collected and dried affording 0.279 g (76.7%) of blue solid.

N²-Phosphinylamidine Metal Salt Complex Synthesis19—[N¹-(2-n-propylphenyl)-N²-(diphenylphosphino)-N²-methyl-4-methylbenzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex C4)

Procedure as described for NP Amidine Metal Salt Complex C3 using thefollowing amounts:N¹-(2-n-propylphenyl)-N²-(diphenylphosphino)-N²-methyl-4-methylbenzamidine(NSP Amidine IV, 0.243 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500mmol). The resulting green solution was stirred overnight at roomtemperature and taken to dryness, yielding 0.344 g of green product(94.0%).

N²-Phosphinylamidine Metal Salt Complex Synthesis20—[N¹-(2-(dimethylamino)ethyl)-N²-(diisopropylphosphino)benzamidine]CrCl₃(NP Amidine Metal Salt Complex D1)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts and modifications:N¹-(2-(dimethylamino)ethyl)-N¹-(diisopropylphosphino)benzamidine (NPAmidine XIX, 0.207 g, 0.673 mmol), CrCl₃(THF)₃ (0.252 g, 0.673 mmol).The ligand was preweighed in a disposable pipet and washed into a vialwith 10 mL of diethyl ether. The ligand solution was added dropwise toCrCl₃(THF)₃ dissolved in 15 mL of THF. The resulting blue-green solutionwas stirred for 30 minutes at room temperature and taken to dryness. Theresidue was dissolved in 3 mL of THF and recrystallized via pentanediffusion to yield 0.271 g (86.4%) of crystalline blue solid. Anal.Calc. (Found) for C₁₇H₃₀N₃PCrCl₃: C, 43.84 ( ); H, 6.49 ( ); N, 9.02 ().

N²-Phosphinylamidine Metal Salt Complex Synthesis21—[N¹-(2-(dimethylamino)ethyl)-N²-(diphenylphosphino)benzamidine]CrCl₃(NP Amidine Metal Salt Complex D2)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts and modifications:N¹-(2-(dimethylamino)ethyl)-N²-(diphenylphosphino)benzamidine (NPAmidine XX, 0.200 g, 0.534 mmol), CrCl₃(THF)₃ (0.200 g, 0.534 mmol). Theresulting blue-green solution was stirred overnight at room temperatureand taken to dryness. The residue was dissolved in 3 mL of THF andrecrystallized via pentane diffusion to yield 0.254 g (89.1%) of darkcrystalline solid. Anal. Calc. (Found) for C₂₃H₂₆N₃PCrCl₃: C, 51.75 ( );H, 4.91 ( ); N, 7.87 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis22—[N²-(diphenylphosphino)-N¹-(2-(diphenylphosphino)ethyl)benzamidine]CrCl₃(NP Amidine Metal Salt Complex D3)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts and modifications:N²-(diphenylphosphino)-N¹-(2-(diphenylphosphino)ethyl)benzamidine (NPAmidine XXII, 0.276 g, 0.534 mmol), CrCl₃(THF)₃ (0.200 g, 0.534 mmol).The resulting blue-green solution was stirred for 3 hours at roomtemperature, taken to dryness, washed with 10 mL of n-pentane and driedto yield 0.364 g of green product (91.2%), which analyzed as a THFsolvate. Anal. Calc. (Found) for C₃₇H₃₈ON₂P₂CrCl₃: C, 59.49 (58.24); H,5.13 (5.12); N, 3.75 (3.85).

N²-Phosphinylamidine Metal Salt Complex Synthesis23—[N²-(diisopropylphosphino)-N¹-(2-(phenylthio)phenyl)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex D4)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts

and modifications:N²-(diisopropylphosphino)-N¹-(2-(phenylthio)phenyl)benzamidine (NPAmidine XXIII, 0.136 g, 0.323 mmol), CrCl₃(THF)₃ (0.121 g, 0.323 mmol).The resulting blue solution was stirred for 1 hour at room temperature.After the volatiles were removed in vacuo, the residue was washed withn-pentane and dried affording 0.202 g (96%) of blue solid. Anal. Calc.(Found) for C₂₉H₃₇ON₂PSCrCl₃: C, 53.50 ( ); H, 5.73 ( ); N, 4.30 ( ); S,4.93 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis24—[N²-(diphenylphosphino)-N¹-(2-(phenylthio)phenyl)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex D5)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts and modifications:N²-(diphenylphosphino)-N¹-(2-(phenylthio)phenyl)benzamidine (NP AmidineXXIV, 0.395 g, 0.809 mmol), CrCl₃(THF)₃ (0.303 g, 0.809 mmol). Theresulting blue-green solution was stirred overnight at room temperatureand taken to dryness, yielding 0.608 g of blue product (99.5%), whichanalyzed as a THF hemisolvate. Anal. Calc. (Found) forC₃₇H₃₇O_(1.5)N₂PSCrCl₃: C, 58.85 (57.63); H, 4.94 (5.20); N, 3.71(3.61); S, 4.25 (3.87).

N²-Phosphinylamidine Metal Salt Complex Synthesis25—[N²-(diisopropylphosphino)-N¹-(2-morpholinoethyl)benzamidine]CrCl₃(NP Amidine Metal Salt Complex D6)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts and modifications:N²-(diisopropylphosphino)-N¹-(2-morpholinoethyl)benzamidine (NP AmidineXXV, 0.187 g, 0.535 mmol), CrCl₃(THF)₃ (0.252 g, 0.673 mmol). Theresulting blue-green solution was stirred for 30 minutes at roomtemperature and taken to dryness. The residue was washed with 3 mL ofMeCN and dried to yield 0.231 g (85.1%) of blue solid. Anal. Calc.(Found) for C₁₉H₃₂ON₃PCrCl₃: C, 44.94 ( ); H, 6.35 ( ); N, 8.27 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis26—[N¹-(2-morpholinoethyl)-N²-(diphenylphosphino)benzamidine]CrCl₃ (NPAmidine Metal Salt Complex D7)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts and modifications:N¹-(2-morpholinoethyl)-N²-(diphenylphosphino)benzamidine (NP AmidineXXVI, 0.222 g, 0.534 mmol), CrCl₃(THF)₃ (0.200 g, 0.534 mmol). Theresulting blue-green solution was stirred overnight at room temperatureand taken to dryness. The residue was dissolved in 3 mL of THF andrecrystallized via pentane diffusion to yield 0.222 g (72.2%) of bluesolid. Anal. Calc. (Found) for C₂₃H₂₈ON₃PCrCl₃: C, 52.14 ( ); H, 4.90 (); N, 7.30 ( ).

N²-Phosphinylamidine Metal Salt Complex Synthesis27—[4-methyl-N²-(diphenylphosphino)-N¹-(thiazol-2-yl)benzamidine](THF)CrCl₃(NP Amidine Metal Salt Complex D8)

Procedure as described for NP Amidine Metal Salt Complex B1 using thefollowing amounts and modifications:4-methyl-N²-(diphenylphosphino)-N¹′-(thiazol-2-yl)benzamidine (NPAmidine XXVII, 0.194 g, 0.500 mmol), CrCl₃(THF)₃ (0.187 g, 0.500 mmol).The resulting green solution was stirred overnight at room temperature,depositing a green solid. The solid was collected and dried affording0.176 g (55.7%). Anal. Calc. (Found) for C₂₇H₂₈ON₃PSCrCl₃: C, 51.32 ( );H, 4.47 ( ); N, 6.65 ( ); S, 5.07 ( ).

TABLE 15 N²-Phosphinylamidine Compounds, Metal Salts, and ProductN²-Phosphinylamidine Metal Salt Complexes of N²-Phosphinylamidine MetalSalt Syntheses 1-27. N²-Phosphinyl Amidine Run # N²-Phosphinyl AmidineMetal Salt Metal Salt Complex N²-Phosphinyl- amidine Metal SaltSynthesis  1

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis  2

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis  3

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis  4

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis  5

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis  6

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis  7

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis  8

N²-Phosphinyl- amidine Metal Salt Synthesis  9

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 10

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 11

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 12

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 13

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 14

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 15

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 16

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 17

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 18

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 19

CrCl₃(THF)₃

N²-Phosphinyl- amidine Metal Salt Synthesis 20

N²-Phosphinyl- amidine Metal Salt Synthesis 21

N²-Phosphinyl- amidine Metal Salt Synthesis 22

N²-Phosphinyl- amidine Metal Salt Synthesis 23

N²-Phosphinyl- amidine Metal Salt Synthesis 24

N²-Phosphinyl- amidine Metal Salt Synthesis 25

N²-Phosphinyl- amidine Metal Salt Synthesis 26

N²-Phosphinyl- amidine Metal Salt Synthesis 27

N²-Phosphinyl-Amidine Metal Salt Complexes

Table 16 provides additional N²-phosphinylamidine metal salt complexesprepared utilizing the methods described herein.

TABLE 16 Additional N²-Phosphinyl-Amidine Metal Salt Complexes (NPAmidine Metal Salt Complexes)

B16

B17

B18

B19

B20

B21

B22

B23

B24

B25

B26

B27

B28

B29

B30

B31

B32

B33

B34

B35

B36

B37

B38

B39

B40

B41

B42

B43

B44

B45

B46

B47

B48

B49

B50

B51

B52

B53

B54

B55

B56

B57

B58

B59

B60

B61

B62

B63

B64

B65

B66

B67

B68

B69

B70

B71

B72

B73

B74

B75

B76

B77

B78

B79

B80

B81

C5

C6

C7

C8

C9

C10

C11

C12

Olefin Oligomerization

The N²-phosphinylamidinecompounds and N²-phosphinylamidine metal saltcomplexes were utilized as prepared using the methods described herein.The MMAO-3A was utilized as obtained from the chemical supplier. Thesolvents were dried and/or purified using conventional methods andstored under conditions to limit their ability to pick-up water. In theproduct analyses, reference to an amount of C₆ or C₈ products refer toall oligomerization products having 6 or 8 carbon atoms, respectively.References to weight percent of 1-hexene or 1-octene refer to the weightpercent of 1-hexene or 1-octene in the C₆ or C₈ product portion,respectively (e.g product purities).

Example 1 Ethylene Oligomerization Run 1

A 1L stainless steel reactor was dried under vacuum at 110° C. for atleast 8 hours prior to use. The reactor was then cooled to roomtemperature and opened to the atmosphere. A flame-sealed glass NMR tube(Wilmad 505-PS) containing NP Amidine Metal Salt Complex B1 (10 mgcomplex, 0.014 mmol, 0.7 mg Cr) and ethylbenzene (1.5 g) was attached tothe cooling coil near the pneumatic stirrer such that the tube wouldbreak upon stirring initiation. The reactor was closed, evacuated andwarmed to 40° C. A solution of cyclohexane (400 mL) and MMAO-3A (1.1 g,6.7 wt % Al solution in heptanes) was then charged into the reactoralong with ethylene (˜400 psi). The stirrer was activated to break theNMR tube, after which the ethylene pressure was increased to 850 psigand fed on-demand. The reaction was allowed to proceed for 30 minutes(starting from the introduction of ethylene) at 40° C. After 30 minutes,water cooling was applied to the reactor system. Once the temperaturereached 35° C., the unreacted ethylene and hydrogen gas was vented tothe atmosphere. A liquid sample was collected and analyzed by GC-FID;for this run ethylbenzene was used as the internal standard. Solids(˜1.0 g) were collected by filtering the solution and cleaning thereactor walls and cooling coil.

Ethylene Oligomerization Run 2

A 0.5L stainless steel reactor was dried under vacuum at 110° C. for atleast 8 hours prior to use. The reactor was then cooled to roomtemperature and opened to the atmosphere. A flame-sealed glass NMR tube(Wilmad 505-PS) containing NP Amidine I (5 mg, 0.012 mmol), Cr(acac)₃ (2mg, 0.006 mmol, 0.3 mg Cr), ethylbenzene (0.8 g) and C9 (0.5 g, internalstandard) was attached to the cooling coil near the pneumatic stirrersuch that the tube would break upon stirring initiation. The reactor wasclosed, evacuated and warmed to 50° C. A solution of cyclohexane (150mL) and MMAO-3A (1.5 g, 6.7 wt % Al solution in heptanes) was thencharged into the reactor along with ethylene (˜400 psi) and hydrogen (50psig). The stirrer was activated to break the NMR tube, after which theethylene pressure was increased to 850 psig and fed on-demand Thereaction was allowed to proceed for 30 minutes (starting from theintroduction of ethylene) at 50° C. After 30 minutes, water cooling wasapplied to the reactor system. Once the temperature reached 35° C., theunreacted ethylene gas was vented to the atmosphere. A liquid sample wascollected and analyzed by GC-FID. Solids (<1.0 g) were collected byfiltering the solution and cleaning the reactor walls and cooling coil.

Ethylene Oligomerization Run 3—Standard Method

A 1L stainless steel reactor was dried under vacuum at 110° C. for atleast 8 hour prior to use. The reactor was then cooled to 50° C. In thedrybox, a 20 mL glass vial was charged with NP Amidine Metal SaltComplex B2 (10 mg complex, 0.014 mmol, 0.7 mg Cr) and ethylbenzene (1.5g). MMAO-3A (3.3 g, 6.7 wt % Al solution in heptanes) was added to theblue heterogeneous solution resulting in formation of a yellow solution.The yellow solution was then added to 0.5 L glass charger containing 400ml cyclohexane. This solution was removed from the drybox and chargedinto the reactor. Hydrogen (50 psig) was added followed by ethylene (850psig, fed on-demand) The reaction was allowed to proceed for 30 minutes(starting from the introduction of ethylene) at 50° C. After 30 minutes,water cooling was applied to the reactor system. Once the temperaturereached 35° C., the unreacted ethylene and hydrogen gas was vented tothe atmosphere. A liquid sample was collected and analyzed by GC-FID;for this run ethylbenzene was used as the internal standard. Solids (1.5g) were collected by filtering the solution and cleaning the reactorwalls and cooling coil.

Ethylene Oligomerization Run 4

A 1L stainless steel reactor was dried under vacuum at 110° C. for atleast 8 h prior to use. The reactor was then cooled to 50° C. In thedrybox, a 20 mL glass vial was charged with NP Amidine IV (15 mg, 0.037mmol), Cr(acac)₃ (6.0 mg, 0.017 mmol, 0.9 mg Cr) and ethylbenzene (2.0g). MMAO-3A (2.9 g, 6.7 wt % Al solution in heptanes) and none (0.50 g,internal standard) were added resulting in formation of a yellowhomogeneous solution. The yellow solution was then added to glasscharger containing 400 ml cyclohexane. This solution was removed fromthe drybox and charged into the reactor. Hydrogen (50 psig) was addedfollowed by ethylene (850 psig, fed on-demand). The reaction was allowedto proceed for 30 minutes (starting from the introduction of ethylene)at 50° C. After 30 minutes, water cooling was applied to the reactorsystem. Once the temperature reached 35° C., the unreacted ethylene andhydrogen gas was vented to the atmosphere. A liquid sample was collectedand analyzed by GC-FID. Solids (4.5 g) were collected by filtering thesolution and cleaning the reactor walls and cooling coil.

TABLE 17 Results of Olefin Oligomerization Runs 1-4 C₆ + C₈ SolidsActivity C₆ 1-hexene C₈ 1-octene Run # (wt. %) (g/g Cr) (wt. %) (wt. %)(wt. %) (wt. %) 1 12 9,500 68.1 93.2 30.2 97.6 2 100 trace — — — — 3 362,000  79.3 96.9 18.7 98.5 4 58 3,200 64.2 94.9 24.5 98.3

Oligomerization Procedure—Oligomerization Runs 5-106

A 1L stainless steel reactor was dried under vacuum at 110° C. for atleast 8 hour prior to use. The reactor was then cooled to 50° C. In adrybox, a 20 mL glass vial was charged with an N²-phosphinyl amidinemetal complex (NP Amidine Metal Salt Complex), catalyst system solvent,and MMAO-3A (6.7 wt % Al solution in heptanes). This solution was thenadded to 0.5 L glass charger containing the bulk oligomerizationsolvent. The combined solution was removed from the drybox and chargedinto the 1 L stainless steel reactor. The reactor was then charged withhydrogen and ethylene charged to the reactor on-demand. The identity ofthe N²-phosphinyl amidine metal salt complex, the amount of the complex,the catalyst solvent, the oligomerization solvent, the amount of theoligomerization solvent, the hydrogen pressure, the ethylene pressure,the oligomerization time and oligomerization pressure for ethyleneoligomerization runs 5-26 and 27-106 are provided in Table 18 and Table20, respectively. The reaction was allowed to proceed at thetemperatures and for the times indicated in Table 18 and Table 20,respectively.

At reaction completion, water cooling was applied to the 1L stainlesssteel reactor. When the reactor temperature reached 35° C., theunreacted ethylene and hydrogen gas was vented to the atmosphere. Aliquid sample was then collected and analyzed by GC-FID. The reactorsolids were collected by filtering the reaction and cleaning the reactorwalls and cooling coil. The product analysis of the products of theethylene oligomerization runs 5-26 and 27-106 are provided in Table 19and Table 21, respectively.

TABLE 18 N²-Phosphinyl Amidine Complex, Catalyst System Ratios, andReaction Condition for Ethylene Oligomerization Runs 5-26. NP AmidineCatalyst Reaction Ethylene Reaction Run Metal Salt System ComplexComplex Cr Al:Cr Bulk Time Pressure Hydrogen Temp. # Complex Solvent^(†)(mg) (mmol) (g) ratio Solvent^(‡) (min) (psi) Pressure (° C.) 5 B2 EB 100.014 0.7 600 0.4 L, cyH 30 850 50 50 6 B4 EB 10 0.013 0.7 600 0.4 L,cyH 30 850 50 50 7 B4 EB 10 0.013 0.7 600 0.4 L, cyH 90 850 50 50 8 B4DCM 15 0.020 1.0 600 0.4 L, cyH 30 850 50 50 9 B4 DCM 15 0.020 1.0 6000.4 L, cyH 60 850 50 50 10 B4 DCM 15 0.020 1.0 600 0.4 L, cyH 120 850 5050 11 B2 DCM 35 0.048 2.5 450 0.4 L, cyH 30 850 50 50 12 B2 DCM 11 0.0150.8 550 0.4 L, cyH 30 850 50 50 13 B2 DCM 6 0.008 0.4 1000 0.4 L, cyH 90850 50 50 14 B2 DCM 6 0.008 0.4 1000 0.4 L, cyH 30 850 50 40 15 B2 DCM 50.007 0.4 1200 0.4 L, cyH 30 850 50 50 16 B2 DCM 5 0.007 0.4 1200 0.4 L,cyH 30 850 50 70 17 B2 DCM 5 0.007 0.4 1200 0.4 L, cyH 30 850 50 90 18B2 DCM 4 0.006 0.3 1500 0.4 L, cyH 180 850 50 50 19 A1 EB 10 0.017 0.9500 0.4 L, cyH 30 850 50 75 20 A3 DCM 6 0.010 0.5 700 0.4 L, cyH 60 85050 50 21 B3 DCM 10 0.015 0.8 500 0.4 L, cyH 30 850 50 60 22 B5 DCM 120.017 0.9 400 0.4 L, cyH 30 850 50 50 23 B5 EB 12 0.017 0.9 400 0.4 L,cyH 30 850 50 50 24 B5 EB 12 0.017 0.9 400 0.4 L, cyH 30 850 50 90 25 B5EB 12 0.017 0.9 400 0.25 L, cyH  30 850 50 120 26 B5 EB 7 0.010 0.5 2000.4 L, cyH 30 850 50 50 ^(†)EB = ethylbenzene, DCM = Dichloromethane^(‡)cyH = cyclohexane

TABLE 19 Product of Ethylene Oligomerization Runs 5-26. Productivitiesand NP Amidine Product Type Activities Product Purities (Wt. %) RunMetal Salt Solid Liquid Solid Carbon Number Distribution (Wt. %) C₆ + C₈C₆ + C₈ 1-hexene MeCp 1-octene # Complex (g) (g) (wt. %) C₆ C₈ C₁₀ C₁₂C₁₄₊ (%) (g/g Cr) (wt. %) (wt. %) (wt. %) 5 B2 1.5 45.4 3 79.3 18.7 0.90.4 0.7 98.0 62,038 96.92 1.17 98.49 6 B4 1.1 52.9 2 76.1 20.1 1.0 0.42.4 96.2 75,077 96.15 1.43 98.51 7 B4 4.4 80.8 5 78.1 20.1 0.9 0.4 0.598.2 117,058 96.48 1.29 98.55 8 B4 NA 7.4 NA 74.5 22.5 1.3 0.8 0.9 97.07,060 95.30 1.61 97.07 9 B4 NA 18.1 NA 74.5 21.9 1.1 0.7 1.8 96.4 17,16195.66 1.54 98.23 10 B4 14.5 31.6 31 75.3 21.8 0.8 0.5 1.6 97.1 30,17895.96 1.47 98.35 11 B2 3.7 30.0 11 77.4 20.5 1.0 0.6 0.5 97.9 11,70196.26 1.36 97.86 12 B2 5.4 18.6 23 77.4 20.3 0.8 0.4 1.1 97.7 23,03596.21 1.35 98.37 13 B2 2.9 41.2 7 77.2 21.2 0.8 0.3 0.5 98.4 94,21496.14 1.44 98.47 14 B2 5.4 13.0 29 72.3 25.3 0.8 0.4 1.2 97.6 29,48694.62 1.98 98.19 15 B2 6.0 13.0 32 76.3 20.5 1.4 0.7 1.1 96.8 35,09395.93 1.42 97.26 16 B2 9.6 14.3 40 83.8 13.4 0.6 0.6 1.6 97.2 38,76298.06 0.65 98.73 17 B2 11.4 12.0 49 88.2 8.0 0.9 0.6 2.3 96.2 32,19398.74 0.32 98.47 18 B2 32.2 29.6 52 75.2 21.3 0.9 0.7 1.9 96.5 99,57296.16 1.43 98.44 19 A1 1.5 12.5 11 83.6 12.5 0.7 0.5 2.7 96.1 13,91897.97 0.68 98.53 20 A3 7.5 3.1 71 71.2 22.0 2.5 1.4 2.9 93.2 5,709 94.061.43 96.10 21 B3 1.8 5.0 26 93.8 2.6 1.4 0.5 1.7 96.4 6,090 98.55 0.0788.76 22 B5 1.6 3.4 32 91.5 2.9 1.3 0.4 3.9 94.4 3,586 98.28 0.09 91.2523 B5 0.5 98.9 0.5 95.9 2.2 1.6 0.1 0.1 98.1 108,407 99.57 0.04 99.32 24B5 1.1 292 0 91.8 0.5 7.2 0.1 0.4 92.3 301,145 99.39 0.01 97.32 25 B546.0 149 24 92.5 1.6 5.3 0.2 0.3 94.1 156,663 99.17 0.04 96.36 26 B5 1.218.1 6 96.4 2.2 1.1 0.1 0.1 98.6 34,185 99.43 0.04 98.03

TABLE 20 N²-Phosphinyl Amidine Complex, Catalyst System Ratios, andReaction Condition for Ethylene Oligomerization Runs 27-106 CatalystReaction Ethylene Reaction Run System Complex Complex Cr Al:Cr Bulk TimePressure Hydrogen Temp. # Complex Solvent^(†) (mg) (mmol) (g) ratioSolvent^(‡) (min) (psi) Pressure (° C.) 27 B12 EB 10 0.0143 0.7 500 0.4L, cyH 30 850 50 50 28 B13 EB 12 0.0191 1.0 500 0.4 L, cyH 30 850 50 5529 B10 EB 7 0.0097 0.5 500 0.4 L, cyH 30 850 50 50 30 B10 EB 10 0.01380.7 600 0.4 L, cyH 30 850 50 55 31 B6  EB 10 0.0146 0.8 500 0.4 L, cyH30 850 50 60 32 B7  EB 10 0.0146 0.8 600 0.4 L, cyH 30 850 50 50 33 B8 EB 10 0.0126 0.7 500 0.4 L, cyH 30 850 50 50 34 B11 EB 9 0.0121 0.6 7000.4 L, cyH 30 850 50 60 35 B11 EB 10 0.0135 0.7 500 0.4 L, cyH 30 850 5050 36 B11 EB 7 0.0094 0.5 500 0.4 L, cyH 30 850 50 50 37 B4  EB 100.0130 0.7 600 0.4 L, cyH 30 850 50 90 38 B11 EB 13 0.0175 0.9 400 0.4L, cyH 30 850 50 90 39 B10 EB 12 0.0166 0.9 400 0.4 L, cyH 30 850 50 9040 B4  EB 10 0.0130 0.7 600 0.4 L, cyH 30 850 50 50 41 B16 EB 10 0.01490.8 400 0.4 L, cyH 30 850 50 50 42 B31 EB 12 0.0170 0.9 400 0.4 L, cyH30 850 50 50 43 B19 EB 12 0.0166 0.9 400 0.4 L, cyH 30 850 50 50 44 B34EB 6 0.0089 0.5 500 0.4 L, cyH 30 850 50 50 45 B34 EB 6 0.0089 0.5 5000.4 L, cyH 30 850 50 60 46 B19 EB 12 0.0166 0.9 400 0.4 L, cyH 30 850 5090 47 B21 EB 12 0.0167 0.9 400 0.4 L, cyH 30 850 50 50 48 B39 EB 60.0089 0.5 500 0.4 L, cyH 30 850 50 60 49 B40 EB 10 0.0135 0.7 600 0.4L, cyH 30 850 50 50 50 B17 EB 13 0.0163 0.9 400 0.4 L, cyH 30 850 50 5051 B41 EB 11 0.0167 0.9 400 0.4 L, cyH 30 850 50 50 52 B35 EB 6 0.00880.5 500 0.4 L, cyH 30 850 50 60 53 B32 EB 13 0.0175 0.9 400 0.4 L, cyH30 850 50 50 54 B39 EB 6 0.0089 0.5 500 0.4 L, cyH 30 850 50 60 55 B15EB 6 0.0081 0.4 500 0.4 L, cyH 30 850 50 60 56 B18 EB 14 0.0170 0.9 4000.4 L, cyH 30 850 50 50 57 B20 EB 11 0.0167 0.9 400 0.4 L, cyH 30 850 5050 58 B24 EB 11 0.0173 0.9 400 0.4 L, cyH 30 850 50 50 59 B14 EB 110.0164 0.9 400 0.4 L, cyH 20 850 50 55 60 B22 EB 6 0.0092 0.5 500 0.4 L,cyH 30 850 50 60 61 B42 EB 11 0.0171 0.9 400 0.4 L, cyH 30 850 50 50 62B43 EB 11 0.0167 0.9 400 0.4 L, cyH 30 850 50 50 63 B23 EB 12 0.0170 0.9400 0.4 L, cyH 30 850 50 50 64 B36 EB 6 0.0092 0.5 400 0.4 L, cyH 30 85050 60 65 C3  EB 12 0.0175 0.9 400 0.4 L, cyH 30 850 50 50 66 B46 EB 120.0177 0.9 400 0.4 L, cyH 30 850 50 50 67 B25 EB 10 0.0149 0.8 400 0.4L, cyH 30 850 50 50 68 B44 EB 12 0.0174 0.9 400 0.4 L, cyH 30 850 50 5069 C1  EB 6 0.0088 0.5 500 0.4 L, cyH 30 850 50 60 70 B45 EB 6 0.00800.4 500 0.4 L, cyH 30 850 50 60 71 B38 EB 6 0.0081 0.4 500 0.4 L, cyH 30850 50 60 72 B56 EB 6 0.0085 0.4 500 0.4 L, cyH 30 850 50 60 73 B31 EB 60.0085 0.4 500 0.4 L, cyH 30 850 50 60 74 B5  EB 6 0.0086 0.4 500 0.4 L,cyH 30 850 50 60 75 B55 EB 6 0.0096 0.5 500 0.4 L, cyH 30 850 50 60 76B26 EB 12 0.0187 1.0 400 0.4 L, cyH 30 850 50 50 77 B47 EB 6 0.0096 0.5500 0.4 L, cyH 30 850 50 60 78 B50 EB 12 0.0158 0.8 400 0.4 L, cyH 30850 50 50 79 B49 EB 6 0.0087 0.5 500 0.4 L, cyH 30 850 50 60 80 B27 EB 60.0088 0.5 500 0.4 L, cyH 30 850 50 60 81 B33 EB 6 0.0080 0.4 500 0.4 L,cyH 30 850 50 60 82 B37 EB 6 0.0089 0.5 500 0.4 L, cyH 30 850 50 60 83B37 EB 6 0.0089 0.5 500 0.4 L, cyH 30 850 50 90 84 B37 EB 6 0.0089 0.5500 0.4 L, cyH 30 850 50 90 85 B5  EB 7 0.0100 0.5 400 0.4 L, cyH 30 5050 90 86 B48 EB 6 0.0101 0.5 500 0.4 L, cyH 30 850 50 60 87 B51 EB 60.0087 0.5 500 0.4 L, cyH 30 850 50 60 88 B41 EB 6 0.0091 0.5 500 0.4 L,cyH 30 850 50 90 89 B29 EB 10 0.0130 0.7 400 0.4 L, cyH 30 850 10 50 90B53 EB 10 0.0143 0.7 400 0.4 L, cyH 30 850 50 50 91 B30 EB 12 0.0171 0.9400 0.4 L, cyH 30 850 50 50 92 B54 EB 12 0.0187 1.0 400 0.4 L, cyH 20850 50 60 93 B52 EB 10 0.0164 0.9 400 0.4 L, cyH 30 850 50 50 94 B28 EB12 0.0166 0.9 400 0.4 L, cyH 30 850 50 70 95 B54 EB 6 0.0093 0.5 400 0.4L, cyH 30 850 50 50 96 B37 EB 6 0.0089 0.5 400 0.4 L, cyH 30 875 25 7097 B41 EB 6 0.0091 0.5 400 0.4 L, cyH 30 875 25 70 98 B25 EB 6.4 0.00960.5 400 0.4 L, cyH 30 850 50 70 99 B25 EB 6.8 0.0102 0.5 400 0.4 L, cyH30 850 50 60 100 B25 EB 6.4 0.0096 0.5 400 0.4 L, cyH 30 850 50 80 101B5  EB 7 0.0100 0.5 400 0.4 L, cyH 30 50 50 60 102 D5  DCM 5 0.007 0.31000 0.4 L, cyH 30 850 50 50 103 D5  DCM 6 0.008 0.4 850 0.4 L, cyH 60850 50 90 104  D5⁻** DCM 5 0.007 0.4 1000 0.4 L, cyH 60 850 50 90 105D4  DCM 4 0.006 0.3 1000 0.4 L, cyH 30 850 50 50 106 D4  EB 11 0.017 0.9400 0.4 L, cyH 30 850 50 50 ^(†)EB = ethylbenzene. ^(‡)cyH =cyclohexane. ⁻**Complex was the negatively charged Amidinate complex.

TABLE 21 Product of Ethylene Oligomerization Runs 27-106 Productivitiesand NP Amidine Product Type Activities Product Purities (Wt. %) RunMetal Salt Solid Liquid Solid Carbon Number Distribution (Wt. %) C₆ + C₈C₆ + C₈ 1-hexene MeCp 1-octene # Complex (g) (g) (wt. %) C₆ C₈ C₁₀ C₁₂C₁₄₊ (%) (g/g Cr) (wt. %) (wt. %) (wt. %) 27 B12 0.8 2.1 27.6 38.2 13.619.1 10.2 18.9 51.8 1,458 72.47 9.29 71.65 28 B13 1.8 5.5 24.7 45.2 28.49.6 7.4 9.4 73.6 4,080 28.15 29.51 75.37 29 B10 0.8 0.4 66.7 52.7 19.210.7 7.2 10.2 71.9 571 38.81 74.30 74.30 30 B10 1.2 5.6 17.6 51.0 21.18.8 7.8 11.3 72.1 5,615 37.34 24.36 70.50 31 B6  0.4 6.4 5.9 98.9 0.70.5 0.0 0.0 99.6 8,398 99.25 0.08 NA 32 B7  1.6 9.3 14.7 96.8 1.1 1.00.4 0.7 97.9 11,995 99.19 0.06 NA 33 B8  0.7 1.7 29.2 86.3 9.0 3.0 1.00.7 95.3 2,478 90.40 2.23 83.11 34 B11 1.1 98.3 1.1 93.2 5.4 1.1 0.2 0.198.6 153,485 96.09 1.71 94.38 35 B11 0.5 40.6 1.2 90.2 8.7 0.8 0.2 0.198.9 57,227 92.89 3.17 92.64 36 B11 0.2 44.7 0.4 91.8 7.4 0.6 0.1 0.199.2 90,282 94.14 2.74 94.01 37 B4  1.5 8.8 14.6 92.4 5.8 0.8 0.6 0.498.2 12,749 98.61 0.22 94.77 38 B11 1.0 26.7 3.6 93.9 4.8 0.8 0.2 0.398.7 28,891 98.15 0.76 97.64 39 B10 0.5 0.7 41.7 74.0 14.0 5.6 2.9 3.588.0 714 80.78 4.77 78.53 40 B4  2.1 21.9 8.8 79.1 19.8 0.5 0.3 0.3 98.931,953 96.21 1.31 98.34 41 B16 1.1 5.6 16.4 69.2 26.5 1.4 0.8 2.1 95.76,897 96.02 1.26 97.94 42 B31 0.9 34.5 2.5 96.9 1.9 1.0 0.1 0.1 98.838,628 99.60 0.03 98.05 43 B19 12.1 117.2 9.4 45.9 32.2 8.2 6.2 7.5 78.1106,359 31.46 29.94 78.44 44 B34 0.4 11.2 3.4 95.7 1.5 2.1 0.3 0.4 97.223,484 99.50 0.03 98.04 45 B34 0.5 12.3 3.9 97.7 0.4 1.7 0.1 0.1 98.126,029 99.74 0.00 93.54 46 B19 125.0 13.8 90.1 60.3 23.9 7.5 3.2 5.184.2 13,502 83.84 8.06 94.58 47 B21 0.7 0.0 100.0 0.0 0.0 0.0 0.0 0.00.0 0 NA NA NA 48 B39 0.5 67.7 0.7 92.8 6.0 1.0 0.2 0.0 98.8 143,86495.87 2.02 95.62 49 B40 0.7 4.4 13.7 86.4 11.1 1.5 0.9 0.1 97.5 6,09798.30 0.46 95.49 50 B17 0.8 0.0 100.0 0.0 0.0 0.0 0.0 0.0 0.0 0 0.000.00 0.00 51 B41 0.6 126.6 0.5 97.4 0.7 1.8 0.1 0.0 98.1 142,657 99.790.01 98.01 52 B35 0.8 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0.0 0 0.00 0.00 0.0053 B32 0.7 3.9 15.2 88.3 10.9 0.4 0.1 0.3 99.2 4,241 98.55 0.19 97.84 54B39 0.8 109.4 0.7 94.5 4.1 1.3 0.1 0.0 98.6 232,007 97.49 1.13 95.77 55B15 0.8 1.8 30.8 59.3 21.5 6.5 5.3 7.4 80.8 3,436 46.97 21.80 76.66 56B18 0.9 1.9 32.1 76.5 21.9 0.6 0.3 0.7 98.4 2,114 94.18 1.16 97.12 57B20 2.2 1.9 53.7 30.8 23.1 12.2 11.6 22.3 53.9 1,176 52.75 16.66 80.6658 B24 0.7 8.2 7.9 81.8 16.6 0.9 0.5 0.2 98.4 8,986 90.61 4.58 96.20 59B14 0.9 117.5 0.8 93.6 5.0 1.2 0.1 0.1 98.6 135,919 95.88 1.78 94.52 60B22 0.3 0.4 42.9 75.4 20.0 2.2 1.3 1.1 95.4 794 90.44 1.23 NA 61 B42 4.71.6 74.6 50.7 41.2 3.6 2.6 1.9 91.9 1,655 89.24 3.30 96.81 62 B43 0.70.4 63.6 0.0 0.0 0.0 0.0 0.0 0.0 0 0.00 0.00 0.00 63 B23 1.1 0.7 61.152.6 31.1 4.2 4.6 7.5 83.7 662 69.05 10.95 90.36 64 B36 0.1 21.4 0.592.8 6.4 0.6 0.1 0.1 99.2 44,224 99.42 0.08 99.13 65 C3  0.5 1.9 20.888.0 8.8 1.7 1.0 0.5 96.8 2,019 90.71 3.23 84.02 66 B46 0.4 61.5 0.688.7 9.3 1.2 0.5 0.3 98.0 65,586 92.96 3.46 88.34 67 B25 0.9 6.1 12.965.7 31.1 1.2 1.3 0.7 96.8 7,599 96.29 1.21 97.91 68 B44 2.4 1.5 61.554.7 35.2 3.1 2.0 5.0 89.9 1,493 88.42 2.99 94.34 69 C1  0.1 6.2 1.685.8 12.7 0.8 0.2 0.5 98.5 13,408 93.34 3.68 92.52 70 B45 0.2 4.3 4.492.5 5.3 0.4 1.8 0.0 97.8 10,070 93.06 3.93 92.53 71 B38 0.8 0.4 66.756.4 11.2 2.3 30.2 0.0 67.6 641 69.58 14.60 66.12 72 B56 0.3 127.4 0.295.5 0.9 2.0 0.5 1.1 96.4 278,354 99.75 0.03 97.90 73 B31 0.1 9.3 1.196.4 1.3 1.0 0.5 0.8 97.7 20,593 99.18 0.01 88.16 74 B5  21.0 221.8 8.696.1 1.0 2.8 0.1 0.0 97.1 481,285 99.49 0.01 98.76 75 B55 0.1 5.3 1.992.2 6.1 0.2 1.5 0.0 98.3 10,403 96.29 1.65 89.28 76 B26 0.8 1.8 30.858.6 30.5 2.2 5.3 3.4 89.1 1,653 66.28 15.52 84.17 77 B47 39.5 96.2 2.80.6 0.1 0.3 99.0 78,087 99.57 0.06 98.94 78 B50 0.8 16.6 4.6 87.8 10.70.8 0.2 0.5 98.5 19,944 96.26 1.51 95.89 79 B49 0.4 35.0 22.4 20.6 11.510.5 57.4 509 54.79 12.71 76.12 80 B27 1.6 73.7 17.3 4.6 1.8 2.6 91.03,197 78.15 10.15 84.77 81 B33 0.2 0.3 40.0 66.8 17.8 8.8 3.7 2.9 84.6608 83.19 0.00 70.35 82 B37 0.2 270.2 0.1 94.6 0.1 5.0 0.2 0.1 94.7551,970 99.69 0.00 93.27 83 B37 29.1 98.0 0.2 1.4 0.2 0.2 98.2 61,64399.59 0.01 45.43? 84 B37 28.7 96.7 0.6 1.6 0.4 0.7 97.3 60,239 99.350.02 45.87 85 B5  21.6 189.3 10.2 95.7 1.2 3.0 0.1 0.0 96.9 351,35799.68 0.02 98.15 86 B48 3.3 67.6 28.2 1.8 1.0 1.4 95.8 6,025 94.80 1.3796.14 87 B51 68.1 94.7 3.8 1.3 0.1 0.1 98.5 149,007 99.49 0.11 99.08 88B41 11.3 91.2 5.3 1.5 0.7 1.3 96.5 22,963 98.99 0.11 94.72 89 B29 1.511.2 11.8 78.3 20.5 0.5 0.3 0.4 98.8 16,325 96.32 1.36 98.37 90 B53 1.95.1 27.1 74.9 15.9 2.8 3.9 2.5 90.8 6,234 81.61 6.86 80.43 91 B30 3.01.7 63.8 44.2 32.9 6.1 5.9 10.9 77.1 1,477 74.92 9.03 87.56 92 B54 2.3135.5 1.7 94.7 3.8 1.3 0.1 0.1 98.5 137,534 98.13 0.87 95.13 93 B52 4.31.8 70.5 54.4 30.7 9.3 4.3 1.3 85.1 1,794 94.69 0.42 97.69 94 B28 1.22.0 37.5 39.2 23.8 8.8 7.5 20.7 63.0 1,464 46.58 20.73 77.74 95 B54 8.371.7 10.4 94.4 4.5 0.7 0.1 0.3 98.9 146,143 97.54 1.14 93.28 96 B37 5.268.6 7.0 97.6 1.1 1.3 0.0 0.0 98.7 146,057 99.87 0.02 98.23 97 B41 13.3110.3 10.8 97.6 1.0 1.3 0.0 0.1 98.6 229,025 99.89 0.01 98.68 98 B25 5.129.9 14.6 82.8 15.6 1.0 0.4 0.2 98.4 59,161 98.83 0.41 98.98 99 B25 3.425.7 11.7 77.2 19.8 2.2 0.3 0.5 97.0 47,179 98.15 0.70 98.54 100 B2535.1 37.0 48.7 85.0 13.2 1.0 0.3 0.5 98.2 73,061 98.99 0.33 98.94 101B5  0.7 86.9 0.8 96.6 1.7 1.5 0.1 0.1 98.3 163,624 99.49 0.03 98.90 102D5  1.1 2.7 29 94.4 1.9 1.4 0.5 1.8 96.3 7,551 97.75 0.14 71.66 103 D5 5.5 4.8 53 86.9 2.5 2.3 .8 6.5 89.4 10,386 98.01 0.21 83.43 104   D5⁻**32.6 2.2 94 39.3 10.6 10.8 8.9 30.4 2,882 92.31 0.8 89.56 105 D4  0.71.5 32 94.5 1.5 0.8 1.3 1.9 4,507 5.77 0.27 NA 106 D4  .3 .7 15 89.1 0.61.7 0.0 8.6 89.7 1,736 96.9 0 NA

Example 2

The effects of aging the N²-phosphinyl amidine metal salt complex,treating the N²-phosphinyl amidine metal salt complex with a neutralligand, treating the N²-phosphinyl amidine metal salt complex with aneutral ligand, and aging the treated N²-phosphinyl amidine metal saltcomplex with a neutral ligand were investigated. Specifically, referringto Table 21, Run 74 was carried out using a N²-phosphinyl amidine metalsalt complex B55 that had been stored for about 5 months. Run 201 wascarried out using approximately 50 mg of a N²-phosphinyl amidine metalsalt complex B5 that had been stored for about 5 months dissolved in amixture of 0.5 g ethylbenzene and 0.5 g THF. to provide theN²-phosphinyl amidine metal salt complex B58 in a 50/50 mixture of THFand ethylbenzene. B5 Run 101 was carried out using approximately 50 mgof an N²-phosphinyl amidine metal salt complex B5 that had been storedfor about 5 months and then dissolved in 1 g anhydrous tetrahydrofuran(THF). The THF was allowed to evaporate to dryness over 18 hours in adry box, and the resulting blue solid was used immediately. Hereinafterthis is referred to as “THF-treated B5.”

Run 40 was carried out with N²-phosphinyl amidine metal salt complex B4which had been stored for 6 months after preparation. Run 203 wascarried out using B67 which was produced as follows: a 20 mL glass vialwas charged with 7 mg anhydrous pyridine (dried over 4 Å molecularsieves), 31 mg B4, and 2 g methylene chloride. The resulting turquoiseblue solution was allowed to stand for 3 hours, followed by slow solventevaporation forming blue crystals. The crystals were captured prior tototal solvent evaporation and were dried under vacuum.

For ethylene oligomerization runs 201, 202, and 204-214, a 1 L stainlesssteel reactor was dried under vacuum at 110° C. for at least 8 hourprior to use. The reactor was then cooled to 50° C. In a dry box, a 20mL glass vial was charged with an N²-phosphinyl amidine metal saltcomplex, 1 g catalyst system solvent, and MMAO-3A (7.6 wt % Al solutionin heptanes) to provide the desired Al:Cr molar ratio. This solution wasthen added to 0.5 L glass charger containing 400 mL of theoligomerization solvent, cyclohexane. The combined solution was removedfrom the dry box and charged into the 1 L stainless steel reactor.Hydrogen was added to the reactor followed by ethylene (fed on-demand).The identity of the N²-phosphinyl amidine metal salt complex, the amountof the complex, the catalyst solvent, the oligomerization solvent, theamount of the oligomerization solvent, the hydrogen pressure, theethylene pressure, the oligomerization time and oligomerization pressurefor ethylene oligomerization Runs 74, 40, 101, and 201-202 are providedin Table 22. The reaction was allowed to proceed at the temperatures andfor the times indicated in Table 22.

At reaction completion, water cooling was applied to the 1 L stainlesssteel reactor system. Once the temperature reached 35° C., the unreactedethylene and hydrogen gas were vented to the atmosphere. A liquid samplewas collected and analyzed by GC-FID. The reactor solids were collectedby filtering the solution and cleaning the reactor walls and coolingcoils. Table 22 also provides an analysis of the products of ethyleneoligomerization Runs 74, 40, 201-202. The amount of polymer production(g polymer), amount of liquid product (g liquid product), wt % polymer,product distribution (as wt % of liquid product), amount of C₆+C₈product as a wt % of liquid product, catalyst activity (g C₆+C₈/g Cr),wt % 1-hexene in the C₆ product, and wt % 1-octene in the C₈ product,and the weight percent of methylcyclopentane produced.

TABLE 22 Run # 74 201 101 40 202 Catalyst System and OligomerizationConditions Amidine Metal Salt Complex B5 B5 B5 B4 B67 Catalyst SystemSolvent EB EB/THF EB EB EB Complex (mg) 6 7 7 10 10 Complex (mmol)0.0086 0.0100 0.0100 0.0130 0.0130 Cr (mg) 0.45 0.52 0.52 0.68 0.68Al:Cr molar ratio 500 400 400 600 400 Bulk Solvent, cyclohexane (mL) 400400 400 400 400 Reaction Time (min) 30 30 30 30 30 Ethylene Pressure(psi) 850 850 850 850 850 Hydrogen Pressure (psi) 50 50 50 50 50Reaction Temperature (° C.) 60 60 60 50 50 Oligomerization ProductProduct Type Solid/Polymer (g) 21 0 0.7 2.1 0.1 Liquid (g) 221.8 0 86.921.9 15.7 Solid/Polymer (wt %) 8.6 N/A 0.8 8.8 0.6 Carbon NumberDistribution C₆ 96.1 0 96.6 79.1 78.6 C₈ 1 0 1.7 19.8 20.1 C₁₀ 2.8 0 1.50.5 0.5 C₁₂ 0.1 0 0.1 0.3 0.4 C₁₄₊ 0 0 0.1 0.3 0.4 Productivities andActivities C₆ + C₈ (wt %) 97.1 NA 98.3 98.9 98.7 C₆ + C₈ (g/g Cr)481,285 NA 163,624 31,953 22,861 Product Purities 1-Hexene (wt %) 99.49NA 99.49 96.21 96.47 Methylcyclopentane 0.1 NA 0.3 1.31 1.34 1-Octene(wt %) 98.76 NA 98.9 98.34 98.29

Referring to Table 22, the oligomerization runs show the impact that theN²-phosphinyl amidine metal salt metal complex age and the treatment ofthe N²-phosphinyl amidine metal salt with a neutral ligand had onethylene oligomerization.

As can be seen in Table 22, N²-phosphinyl amidine metal salt complexeswhich had been stored for significant periods of time (Run 74, complexB5 stored for 5 months and Run 40, Complex B4, stored for 6 months)prior to preparing the catalyst system produced significant amounts ofpolymer (8.6 wt % and 8.8 wt %, respectively). Table 22 data also showthat N²-phosphinyl amidine metal salt complexes can be treated with aneutral ligand such that the N²-phosphinyl amidine metal salt complexcan then be utilized in a catalyst system which can produce lesspolymer. In Run 101, the N²-phosphinyl amidine metal salt complex thatwas treated with the same neutral ligand as was originally present inthe N²-phosphinyl amidine metal salt complex (i.e., THF), resulted in acatalyst system producing 0.6 wt % polymer. In run 202, theN²-phosphinyl amidine metal salt complex that was treated with adifferent neutral ligand (i.e., pyridine) than was originally present inthe N²-phosphinyl amidine metal salt complex (THF), resulted in acatalyst system producing 0.6 wt % polymer.

Referring to Run 74, the N²-phosphinyl amidine metal salt complex B5,which had been stored for 5 months, produced a catalyst system having aproductivity of 481,285 g(C₆+C₈)/g (Cr). Run 201 shows use of thisN²-phosphinyl amidine metal salt complex in a catalyst system whereinone-half of the normal amount of catalyst solvent, ethylbenzene, wasreplaced with neutral ligand, THF, (as described previously). Thereplacement of one half of the ethylbenzene with THF resulted in aninactive catalyst system. This indicates that a large excess of neutralligand can act as a catalyst system poison. However, isolation ofN²-phosphinyl amidine metal salt complex B5 from a solution containing aneutral ligand (THF), in Run 101, produced an active catalyst systemhaving a reduced productivity (163,624 g (C₆+C₈)/g (Cr)) while producingless polymer (0.8 wt %). Reviewing the effects of aging an N²-phosphinylamidine metal salt complex and treatment of an aged N²-phosphinylamidine metal salt complex have on catalyst system productivity andpolymer production, it can be seen that there are both positive andnegative effects to aging an N²-phosphinyl amidine metal salt complexand that these effects can be balanced to provide an optimum catalystsystem using an N²-phosphinyl amidine metal salt complex. Further, thisexperiment shows that the effects related to the aging of theN²-phosphinyl amidine metal salt complex can be reversed by treatmentwith a neutral ligand.

Additional N²-phosphinyl amidine metal salt complexes were used incatalyst systems for olefin oligomerizations using the methods describedin this example. The oligomerization conditions and product analyses foroligomerization Runs 204-214 are provided in Table 23.

TABLE 23 Run No. 204 205 206 207 208 209 Catalyst System andOligomerization Conditions Amidine Metal Salt Complex B69 B72 B70 B74B75 B76 Complex (mg) 7 5 4 6 6 7 Complex mmol 0.0098 0.0073 0.00570.0091 0.0093 0.0107 Cr (mg) 0.51 0.38 0.30 0.47 0.49 0.55 Al:Cr molarratio 400 800 1000 800 600 400 Catalyst System Solvent, 1 1 1 1 1 1Ethylbenzene (g) Catalyst System Aging Time (hours) 3.5 2 2 2 18 >1Reaction Time (min) 30 30 30 30 30 30 Ethylene Pressure (psi) 850 850850 875 875 850 Hydrogen Pressure (psi) 50 50 50 25 25 50 ReactionTemperature (° C.) 80 70 70 70 70 60 Oligomerization Product ProductType Solid/Polymer (g) 3.4 0.05 0.4 27.3 1.9 1.7 Liquid (g) 228.9 43.12.4 212.1 25.3 263 Solid/Polymer (wt %) 1.5 0.1 14.3 11.4 6.99 0.6Carbon Number Distribution C6 95.2 81.5 63.0 93.9 81.8 96.2 C₈ 1.2 17.132.5 3.2 16.4 0.3 C₁₀ 3.4 1.0 1.6 2.7 1.3 3.4 C₁₂ 0.1 0.3 1.5 0.1 0.30.1 C₁₄₊ 0.1 0.1 1.4 0.1 0.2 0.0 Productivities and Activities C₆ + C₈(wt %) 96.4 98.6 95.5 97.1 98.2 96.5 C₆ + C₈ (g/g Cr) 433,511 111,9797,747 434,368 51,203 458,107 Product Purities 1-Hexene (wt %) 99.7298.72 95.20 99.68 99.01 99.85 Methylcyclopentane 0.02 0.46 1.43 0.060.27 0.00 1-Octene (wt %) 98.64 98.89 97.09 99.34 99.06 96.33 Run No.210 211 212 213 214 Catalyst System and Oligomerization ConditionsAmidine Metal Salt Complex B77 B78 B73 B73 B73 Complex (mg) 8 7 7 7   7Complex mmol 0.0124 0.0099 0.0097   0.0097 0.0097 Cr (mg) 0.64 0.51 0.50 0.50 0.50 Al:Cr molar ratio 800 400 800 800    800 Catalyst SystemSolvent, 1 1 1 1   1 Ethylbenzene (g) Catalyst System Aging Time (hours)1 20 4 2^(‡)  20 Reaction Time (min) 30 15 30 30   15 Ethylene Pressure(psi) 875 875 875 875    875 Hydrogen Pressure (psi) 25 25 25 25   25Reaction Temperature (° C.) 70 70 70 60   70 Oligomerization ProductProduct Type Solid/Polymer (g) 0.04 0.2 2.3 2  0.03 Liquid (g) 230.6274.7 115.8 107.7  47.1 Solid/Polymer (wt %) 0.0 0.07 1.9 1.8 0.1 CarbonNumber Distribution C6 96.1 94.6 66.5 61.6  68.3 C₈ 0.9 1.0 31.1 36.0 29.6 C₁₀ 2.9 4.2 1.2 1.1 0.9 C₁₂ 0.1 0.1 0.7 0.7 0.6 C₁₄₊ 0.0 0.1 0.50.6 0.6 Productivities and Activities C₆ + C₈ (wt %) 97.0 95.6 97.697.6  97.9 C₆ + C₈ (g/g Cr) 346,804 511,598 225,132 209,384     91,851Product Purities 1-Hexene (wt %) 99.83 99.75 97.26 96.54  97.47Methylcyclopentane 0.02 0.02 1.07 1.34 0.94 1-Octene (wt %) 96.49 98.6499.22 99.05  98.80 ^(‡)Catalyst system was aged at 50° C.

Example 3

The effect of aging a catalyst system comprising a metal alkyl and anN²-phosphinyl amidine metal salt complex before contacting the catalystsystem with an olefin, the effect of aging the metal alkyl beforecontacting the metal alkyl with an N²-phosphinyl amidine metal saltcomplex, and the effect that the catalyst system solvent has on variousolefin oligomerization parameters was investigated. The N²-phosphinylamidine metal salt complexes were contacted with a metal alkyl in ethylbenzene at room temperature under the conditions indicated in Table 24.The catalyst system mixture of N²-phosphinyl amidine metal salt complexand metal alkyl was subsequently contacted with ethylene and hydrogenunder the oligomerization process conditions indicated in Table 24 usingthe method described in Example 2. The results demonstrate that varyingthe time in which the metal alkyl and N²-phosphinyl amidine metal saltcomplexes are contacted prior to exposure to a monomer affects both thecatalyst activity and the amount of polymer formation.

TABLE 24 Run No. 301 302 303 304 305 Catalyst System and OligomerizationConditions Amidine Metal Salt Complex B68 B68 B68 B68 B71 Complex (mg) 77 7 7 7 Complex mmol 0.0098 0.0098 0.0098 0.0098 0.0098 Cr (mg) 0.510.51 0.51 0.51 0.51 Al:Cr molar ratio 400 400 400 400 400 CatalystSystem Solvent, Ethylbenzene (g) 1.0 1.0 1.0 1.0 1.0 Metal Alkyl ThermalAging Time (days) — — — — — Catalyst System Aging Time (hours) 0.17 2 1872 16 Reaction Time (min) 30 30 30 30 30 Ethylene Pressure (psi) 850 850850 850 850 Hydrogen Pressure (psi) 50 50 50 50 50 Reaction Temperature(° C.) 60 60 60 60 70 Oligomerization Product Product Type Solid/Polymer(g) 5.8 4.1 0.9 1.9 0.1 Liquid (g) 69.5 169.7 139.6 154.7 316.9Solid/Polymer (wt %) 7.7 2.4 0.6 1.2 0.03 Carbon Number Distribution C₆96.4 95.9 96.5 96.5 92.7 C₈ 2.1 1.7 1.6 1.3 0.6 C₁₀ 1.2 2.3 1.8 2.0 6.3C₁₂ 0.1 0.1 0.1 0.1 0.1 C₁₄₊ 0.2 0.0 0.0 0.1 0.3 Productivities andActivities C₆ + C₈ (wt %) 98.5 97.6 98.1 97.8 93.3 C₆ + C₈ (g/g Cr)134,126 324,506 268,316 296,429 578,445 Product Purities 1-Hexene (wt %)99.69 99.67 99.71 99.57 99.67 Methylcyclopentane 0.03 0.03 0.02 0.040.01 1-Octene (wt %) 98.83 98.86 98.49 98.32 97.95 Run No. 306 307 308309 Catalyst System and Oligomerization Conditions Amidine Metal SaltComplex B71 B72 B72 B72 Complex (mg) 7 4 4 4 Complex mmol 0.0098 0.00580.0058 0.0058 Cr (mg) 0.51 0.30 0.30 0.30 Al:Cr molar ratio 400 500 500500 Catalyst System Solvent, Ethylbenzene (g) 1.0 0.5 1.5 0.5 MetalAlkyl Thermal Aging Time (days) 6 — — — Catalyst System Aging Time(hours) 16 48 48 3 Reaction Time (min) 30 30 30 30 Ethylene Pressure(psi) 850 850 850 850 Hydrogen Pressure (psi) 50 50 50 50 ReactionTemperature (° C.) 70 70 70 70 Oligomerization Product Product TypeSolid/Polymer (g) 0.8 2.1 2.5 2.6 Liquid (g) 312.9 119.2 86.7 21.9Solid/Polymer (wt %) 0.3 1.7 2.8 10.6 Carbon Number Distribution C₆ 93.783.6 83.7 85.3 C₈ 0.9 14.2 14.5 13.2 C₁₀ 5.2 1.7 1.4 1.0 C₁₂ 0.1 0.5 0.30.3 C₁₄₊ 0.1 0.0 0.1 0.2 Productivities and Activities C₆ + C₈ (wt %)94.6 97.8 98.2 98.5 C₆ + C₈ (g/g Cr) 579,101 383,977 280,428 71,051Product Purities 1-Hexene (wt %) 99.70 98.97 98.97 98.89Methylcyclopentane 0.01 0.33 0.33 0.31 1-Octene (wt %) 98.55 98.91 98.9098.44

Runs 301-304, 307, and 309 show the effect that aging the catalystsystem containing MMAO and the N²-phosphinyl amidine metal salt complexB68 at room temperature had on an ethylene oligomerization. Aging thecatalyst system increases the productivity of the catalyst system anddecreases the weight percentage of polymer formed.

Runs 305 and 306 show the effect that thermal aging of the metal alkyl(MMAO) has on an ethylene oligomerization. In these two runs, anethylene oligomerization was performed using a first catalyst systemwhich was prepared using MMAO as it was supplied (Run 305) and wascompared to an ethylene oligomerization that was performed using asecond catalyst system using MMAO which had been “thermally aged” at 55°C. for 6 days in a sealed vial under a dry nitrogen atmosphere (Run306). In each instance, the catalyst system was prepared using theN²-phosphinyl amidine metal salt complex B71 and the catalyst system wasaged at room temperature in ethylbenzene for 16 hours before beingcontacted with ethylene and hydrogen under the conditions indicated inTable 24. Surprisingly, it was observed that the oligomerizationcatalyst system using the thermally-aged MMAO produced less polymerproduct than the oligomerization catalyst system comprising thenon-thermally aged MMAO. In both instances the catalyst systemsdisplayed comparable catalyst system productivities.

Runs 307-308 show the effects that the amount of catalyst system solventcan have on a catalyst system containing a metal alkyl and anN²-phosphinyl amidine metal salt complex mixture. Specifically,increasing the quantity of the catalyst system solvent (ethylbenzene)reduces the catalyst system productivity and increases the weightpercentage of polymer formed during ethylene oligomerization.

The results demonstrate that the catalyst system activity and polymerformation can be altered by thermally aging the metal alkyl, aging thecatalyst system containing a metal alkyl and an N²-phosphinyl metal saltcomplex, and/or adjusting the amount of solvent in which the catalystsystem is prepared.

Example 4

The solubility of several N²-phosphinyl amidine metal salt complexes inethylbenzene was investigated. N²-phosphinyl amidine metal saltcomplexes B25, B5, B72, and B68 were prepared using the methodologiesdescribed herein. The structures of these complexes are presented inTable 25. The solubility of each complex was determined by charging a 20mL glass vial with 10 mg of the N²-phosphinyl amidine metal salt complex(blue) and 1.0 g of ethylbenzene. The solutions were then mixed andallowed to stand. If the ethylbenzene remained colorless, theN²-phosphinyl amidine metal salt complex was considered insoluble. Ifthe ethylbenzene turned light blue but observable solids remained in thevial, the N²-phosphinyl amidine metal salt complex was consideredslightly soluble. If all the solids dissolved and the solution turnedblue, the N²-phosphinyl amidine metal salt complex was consideredsoluble. The results of this solubility testing are shown below.

TABLE 25

Comparing the solubility of N²-phosphinyl amidine metal salt complex B25to the solubility of N²-phosphinyl amidine metal salt complex B72, andthe solubility of N²-phosphinyl amidine metal salt complex B5 to thesolubility of N²-phosphinyl amidine metal salt complex B78, it can beseen that having a substituent group in the 4-position of an aromaticgroup attached to the N¹ nitrogen atom of an N²-phosphinyl amidine metalsalt complex increases the solubility of the N²-phosphinyl amidine metalsalt complex in an aromatic solvent.

While preferred embodiments of the invention have been shown anddescribed, modifications thereof can be made by one skilled in the artwithout departing from the spirit and teachings of the disclosure. Theembodiments described herein are exemplary only, and are not intended tobe limiting. Many variations and modifications of the disclosure arepossible and are within the scope of the invention. Use of the term“optionally” with respect to any element of a claim is intended to meanthat the subject element is required, or alternatively, is not required.Both alternatives are intended to be within the scope of the claim. Useof broader terms such as comprises, includes, having, etc. should beunderstood to provide support for narrower terms such as consisting of,consisting essentially of, comprised substantially of, etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present invention. Thus, the claims are a further description andare an addition to the preferred embodiments of the present invention.The discussion of a reference in the Background is not an admission thatit is prior art to the present invention, especially any reference thatmay have a publication date after the priority date of this application.The disclosures of all patents, patent applications, and publicationscited herein are hereby incorporated by reference, to the extent thatthey provide exemplary, procedural or other details supplementary tothose set forth herein.

1. An N²-phosphinyl amidine compound characterized by having theformula:

wherein: R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆to C₂₀ substituted aryl group, R² is a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups, R³ is hydrogen, a C₁to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, and R⁴ and R⁵ are eachindependently a C₁ to C₃₀ organyl group consisting essentially of inertfunctional groups.
 2. A method of preparing an N²-phosphinyl amidinecompound according to claim 1, characterized by having the formula:

wherein: R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloakyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆to C₂₀ substituted aryl group, R² is a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups, R³ is hydrogen, a C₁to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, and R⁴ and R⁵ are eachindependently a C₁ to C₃₀ organyl group consisting essentially of inertfunctional groups, comprising: a) contacting a metal amide with anitrile under conditions capable of forming a metal amidinate; and b)contacting a phosphine halide with the metal amidinate under conditionscapable of forming a compound comprising an N²-phosphinyl amidine group.3. A metal salt complex of an N²-phosphinyl amidine compound accordingto claim 1, characterized by having the formula:

wherein: R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆to C₂₀ substituted aryl group, R² substituted cycloalkyl group, a to C₆to C₂₀ aryl group, or a to C₆ to C₂₀ substituted aryl group, R² is a C₁to C₃₀ organyl group consisting essentially of inert functional groupsR³ is hydrogen a C₁ to C₃₀ organyl group, or a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups, R⁴ and R⁵ are eachindependently a C₁ to C₃₀ organyl group consisting essentially of inertfunctional groups, MX_(p) represents the metal salt where M is atransition metal, X is a monoanion, and p ranges from 2 to 6, Q is aneutral ligand, and a ranges from 0 to
 6. 4. A method of preparing anN²-phosphinyl amidinc metal salt complex according to claim 3,characterized by having the formula:

wherein: R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆to C₂₀ substituted aryl group, R² is a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups R³ is hydrogen, a C₁to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, R⁴ and R⁵ are each independentlya C₁ to C₃₀ organyl group consisting essentially of inert functionalgroups, MX_(p) represents the metal salt where M is a transition metal,X is a monoanion and p ranges from 2 to 6, Q is a neutral ligand, and aranges from 0 to 6, comprising: a) contacting a transition metal saltwith an N²-phosphinyl amidine compound, characterized by having theformula:

wherein: R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆to C₂₀ substituted aryl group, R² is a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups, R³ is hydrogen, a C₁to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, and R⁴ and R⁵ are eachindependently a C₁ to C₃₀ organyl group consisting essentially of inertfunctional groups; and b) forming the N²-phosphinyl amidine metal saltcomplex.
 5. A catalyst system comprising: a) an N²-phosphinyl amidinemetal salt complex according to claim 3 characterized by having theformula:

wherein: R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆to C₂₀ substituted aryl group, R² is a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups R³ is hydrogen, a C₁to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, R⁴ and R⁵ are each independentlya C₁ to C₃₀ organyl group consisting essentially of inert functionalgroups, MX_(p) represents the metal salt where M is a transition metal,X is a monoanion and p ranges from 2 to 6, Q is a neutral ligand, and aranges from 0 to 6; and b) a metal alkyl.
 6. A method of preparing acatalyst system according to claim 5, comprising forming a catalystsystem mixture comprising: a) the N²-phosphinyl amidine metal saltcomplex, characterized by having the formula:

wherein: R¹ is a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, aC₄ to C₂₀ substituted cycloalkyl group, a C₆ to C₂₀ aryl group, or a C₆to C₂₀ substituted aryl group, R² is a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups R³ is hydrogen, a C₁to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, R⁴ and R⁵ are each independentlya C₁ to C₃₀ organyl group consisting essentially of inert functionalgroups, MX_(p) represents the metal salt where M is a transition metal,X is a monoanion and p ranges from 2 to 6, Q is a neutral ligand, and aranges from 0 to 6; and h) the metal alkyl.
 7. An olefin oligomerizationprocess comprising: a) contacting an olefin and the catalyst systemaccording to claim 5, wherein the metal alkyl is an aluminoxane; and b)forming an olefin oligomer product.
 8. An olefin oligomerization processcomprising: a) forming a catalyst system mixture according to claim 6,wherein the metal alkyl is an aluminoxane; b) contacting the catalystsystem mixture with an olefin; and c) forming an olefin oligomerproduct. 9-10. (canceled)
 11. The N²-phosphinyl amidine compound ofclaim 1, wherein R¹ is a phenyl group or a substituted phenyl group. 12.The N²-phosphinyl amidine compound of claim 1, wherein R¹ is a phenylgroup, a 2-substituted phenyl group, a 4-substituted phenyl group, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group.13. The N²-phosphinyl amidine compound of claim 1, wherein eachsubstituent of the substituted phenyl group is independently a halide, aC₁ to C₅ alkyl group, or a C₁ to C₅ alkoxy group.
 14. The N²-phosphinylamidine compound of claim 1, wherein R¹ is a phenyl group, a2-methylphenyl group, a 2-ethylphenyl group, a 2-isopropyl group, a2-tert-butylphenyl group, a 4-methylphenyl group, a 4-ethylphenyl group,a 4-isopropyl group, a 4-tert-butylphenyl group, a 2,6-dimethylphenylgroup, a 2,6-diethylphenyl group, a 2,6-diisopropylphenyl group, a2-methyl-6-isopropylphenyl group, a 3,5-dimethylphenyl group, a2,4,6-trimethylphenyl group, or a 2,6-dimethyl-4-tert-butylphenyl group.15. The N²-phosphinyl amidine compound of claim 1, wherein R² is a C₁ toC₁₅ alkyl group, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substitutedcycloalkyl group, a C₃ to C₁₅ aliphatic heterocyclic group, a C₃ to C₁₅substituted aliphatic heterocyclic group, a C₆ to C₂₀ aryl group, a C₆to C₂₀ substituted aryl group, a C₇ to C₂₀ aralkyl group, a C₇ to C₂₀substituted aralkyl group, a C₃ to C₂₀ heteroaryl group, or a C₃ to C₂₀substituted heteroaryl group.
 16. The N²-phosphinyl amidine compound ofclaim 1, wherein R² is a C₆ to C₂₀ phenyl group or a C₆ to C₂₀substituted phenyl group.
 17. The N²-phosphinyl amidine compound ofclaim 1, wherein R² is a C₆ to C₂₀ benzyl group, a C₆ to C₂₀ substitutedbenzyl group, a C₆ to C₂₀ ethylphenyl group, or a C₆ to C₂₀ substitutedethylphenyl group.
 18. The N²-phosphinyl amidine compound of claim 1,wherein R³ is hydrogen, a C₁ to C₁₀ alkyl group, a C₁ to C₁₅ cycloalkylgroup, a C₁ to C₁₅ substituted cycloalkyl group, a C₃ to C₁₅ aliphaticheterocyclic group, a C₃ to C₁₅ substituted aliphatic heterocyclicgroup, a C₆ to C₁₅ aryl group, a C₆ to C₁₅ substituted aryl group, a C₃to C₁₅ heteroaryl group, or a substituted C₃ to C₁₅ heteroaryl group.19. The N²-phosphinyl amidine compound of claim 1, wherein R³ ishydrogen.
 20. The N²-phosphinyl amidine compound of claim 1, wherein R⁴and R⁵ are independently a C₁ to C₁₅ alkyl group, a C₄ to C₂₀ cycloalkylgroup, a C₄ to C₂₀ substituted cycloalkyl group, a C₃ to C₁₅ aliphaticheterocyclic group, a C₃ to C₁₅ substituted aliphatic heterocyclicgroup, a C₆ to C₂₀ aryl group, a C₆ to C₂₀ substituted aryl group, a C₃to C₂₀ heteroaryl group, or a C₃ to C₂₀ substituted heteroaryl group.21. The N²-phosphinyl amidine compound of claim 1, wherein R⁴ and R⁵ areindependently a methyl group, an ethyl group, an isopropyl group, atert-butyl group, or a neopentyl group.
 22. The N²-phosphinyl amidinecompound of claim 1, wherein R⁴ and R⁵ are each independently acyclopentyl group, a substituted cyclopentyl group, a cyclohexyl group,or a substituted cyclohexyl group.
 23. The N²-phosphinyl amidinecompound of claim 1, wherein R⁴ and R⁵ are independently a phenyl groupor a substituted phenyl group.
 24. The N²-phosphinyl amidine compound ofclaim 1, wherein R⁴ and R⁵ are independently a phenyl group, a2-substituted phenyl group, a 4-substituted phenyl group, a2,4-disubstituted phenyl group, a 2,6-disubstituted phenyl group, a3,5-disubstituted phenyl group, or a 2,4,6-trisubstituted phenyl group.25. The N²-phosphinyl amidine compound of claim 1, wherein R¹ is aphenyl group or a substituted phenyl group, R² is a C₁ to C₁₅ alkylgroup, a C₄ to C₂₀ cycloalkyl group, a C₄ to C₂₀ substituted cycloalkylgroup, a C₆ to C₂₀ aryl group, a C₆ to C₂₀ substituted aryl group, a C₇to C₂₀ aralkyl group, or a C₇ to C₂₀ substituted aralkyl group, R³ ishydrogen, and R⁴ and R⁵ are independently a C₁ to C₁₅ alkyl group, a C₄to C₂₀ cycloalkyl group, a C₄ to C₂₀ substituted cycloalkyl group, a C₆to C₂₀ aryl group, or a C₆ to C₂₀ substituted aryl group. 26-58.(canceled)
 59. An N²-phosphinyl amidine compound characterized by havingthe formula:

wherein: is a C₁ to C₃₀ organyl group, R² is a C₁ to C₃₀ organyl groupconsisting essentially of inert functional groups, R³ is hydrogen, a C₁to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, and R⁴ and R⁵ are eachindependently a C₁ to C₃₀ organyl group consisting essentially of inertfunctional groups, wherein R¹ comprises a metal complexing group and alinking group linking the metal complexing group to the N¹ nitrogen atomof an N²-phosphinyl amidine group of the N²-phosphinyl amidine compoundcharacterized by having the formula

wherein Q¹ represents the metal complexing group and is a dialkyl aminylgroup, a dicycloalkyl aminyl group, a di(substituted cycloalkyl) aminylgroup, an N-(alkyl)-N-(cycloalkyl) aminyl group, anN-(alkyl)-N-(substituted cycloalkyl) aminyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) aminyl group, a diaryl aminylgroup, a di(substituted aryl) aminyl group, an N-aryl-N-(substitutedaryl) aminyl group, an N-alkyl-N-aryl aminyl group, anN-alkyl-N-(substituted aryl) aminyl group, a dialkyl phosphinyl group, adicycloalkyl phosphinyl group, a di(substituted cycloalkyl) phosphinylgroup), an N-(alkyl)-N-(cycloalkyl) phosphinyl group, anN-(alkyl)-N-(substituted cycloalkyl) phosphinyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) phosphinyl group, a diarylphosphinyl group, a di(substituted aryl) phosphinyl group, aP-aryl-P-(substituted aryl) phosphinyl group, a P-alkyl-P-arylphosphinyl group, a P-alkyl-P-(substituted aryl) phosphinyl group, analkyl etheryl group, an aryl etheryl group, a substituted aryl etherylgroup, an alkyl sulfidyl group, an aryl sulfidyl group, a substitutedaryl sulfidyl group, a furanyl group, a substituted furanyl group, athienyl group, a substituted thienyl group, a tetrahydrofuranyl group, asubstituted tetrahydrofuranyl group, a thiophanyl group, a substitutedthiophanyl group, a pyridinyl group, a substituted pyridinyl group, amorphilinyl group, a substituted morphilinyl group, a pyranyl group, asubstituted pyranyl group, a tetrahydropyranyl group, a substitutedtetrahydropyranyl group, a quinolinyl group, a substituted quinolinylgroup, a pyrrolyl group, a substituted pyrrolyl group, a pyrrolidinylgroup, a substituted pyrrolidinyl group, a piperidinyl group, or asubstituted piperidinyl group.
 60. A method of preparing theN²-phosphinyl amidine compound, characterized by having the formula:

wherein: R¹ is a C₁ to C₃₀ organyl group, R² is a C₁ to C₃₀ organylgroup consisting essentially of inert functional groups, R³ is hydrogen,a C₁ to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, and R⁴ and R⁵ are eachindependently a C₁ to C₃₀ organyl group consisting essentially of inertfunctional groups, comprising: a) contacting a metal amide with anitrile under conditions capable of forming a metal amidinate; and b)contacting a phosphine halide with the metal amidinate under conditionscapable of forming a compound comprising an N²-phosphinyl amidine group.61. The method of claim 60, wherein R¹ comprises a metal complexinggroup and a linking group linking the metal complexing group to the N¹nitrogen atom of an N²-phosphinyl amidine group of the N²-phosphinylamidine compound characterized by having the formula

wherein Q¹ represents the metal complexing group and is a dialkyl aminylgroup, a dicycloalkyl aminyl group, a di(substituted cycloalkyl) aminylgroup, an N-(alkyl)-N-(cycloalkyl) aminyl group, anN-(alkyl)-N-(substituted cycloalkyl) aminyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) aminyl group, a diaryl aminylgroup, a di(substituted aryl) aminyl group, an N-aryl-N-(substitutedaryl) aminyl group, an N-alkyl-N-aryl aminyl group, anN-alkyl-N-(substituted aryl) aminyl group, a dialkyl phosphinyl group, adicycloalkyl phosphinyl group, a di(substituted cycloalkyl) phosphinylgroup), an N-(alkyl)-N-(cycloalkyl) phosphinyl group, anN-(alkyl)-N-(substituted cycloalkyl) phosphinyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) phosphinyl group, a diarylphosphinyl group, a di(substituted aryl) phosphinyl group, aP-aryl-P-(substituted aryl) phosphinyl group, a P-alkyl-P-arylphosphinyl group, a P-alkyl-P-(substituted aryl) phosphinyl group, analkyl etheryl group, an aryl etheryl group, a substituted aryl etherylgroup, an alkyl sulfidyl group, an aryl sulfidyl group, a substitutedaryl sulfidyl group, a furanyl group, a substituted furanyl group, athienyl group, a substituted thienyl group, a tetrahydrofuranyl group, asubstituted tetrahydrofuranyl group, a thiophanyl group, a substitutedthiophanyl group, a pyridinyl group, a substituted pyridinyl group, amorphilinyl group, a substituted morphilinyl group, a pyranyl group, asubstituted pyranyl group, a tetrahydropyranyl group, a substitutedtetrahydropyranyl group, a quinolinyl group, a substituted quinolinylgroup, a pyrrolyl group, a substituted pyrrolyl group, a pyrrolidinylgroup, a substituted pyrrolidinyl group, a piperidinyl group, or asubstituted piperidinyl group
 62. A metal salt complex of anN²-phosphinyl amidine compound, characterized by having the formula:

wherein: R¹ is a C₁ to C₃₀ organyl group, R² is a C₁ to C₃₀ organylgroup consisting essentially of inert functional groups, R³ is hydrogen,a C₁ to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, and R⁴ and R⁵ are eachindependently a C₁ to C₃₀ organyl group consisting essentially of inertfunctional groups, MX_(p) represents the metal salt where M is atransition metal, X is a monoanion, and p ranges from 2 to 6, Q is aneutral ligand, and a ranges from 0 to 6, wherein R¹ comprises a metalcomplexing group and a linking group linking the metal complexing groupto the N¹ nitrogen atom of an N²-phosphinyl amidine group of theN²-phosphinyl amidine compound characterized by having the formula

wherein Q′ represents the metal complexing group and is a dialkyl aminylgroup, a dicycloalkyl aminyl group, a di(substituted cycloalkyl) aminylgroup, an N-(alkyl)-N-(cycloalkyl) aminyl group, anN-(alkyl)-N-(substituted cycloalkyl) aminyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) aminyl group, a diaryl aminylgroup, a di(substituted aryl) aminyl group, an N-aryl-N-(substitutedaryl) aminyl group, an N-alkyl-N-aryl aminyl group, anN-alkyl-N-(substituted aryl) aminyl group, a dialkyl phosphinyl group, adicycloalkyl phosphinyl group, a di(substituted cycloalkyl) phosphinylgroup), an N-(alkyl)-N-(cycloalkyl) phosphinyl group, anN-(alkyl)-N-(substituted cycloalkyl) phosphinyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) phosphinyl group, a diarylphosphinyl group, a di(substituted aryl) phosphinyl group, aP-aryl-P-(substituted aryl) phosphinyl group, a P-alkyl-P-arylphosphinyl group, a P-alkyl-P-(substituted aryl) phosphinyl group, analkyl etheryl group, an aryl etheryl group, a substituted aryl etherylgroup, an alkyl sulfidyl group, an aryl sulfidyl group, a substitutedaryl sulfidyl group, a furanyl group, a substituted furanyl group, athienyl group, a substituted thienyl group, a tetrahydrofuranyl group, asubstituted tetrahydrofuranyl group, a thiophanyl group, a substitutedthiophanyl group, a pyridinyl group, a substituted pyridinyl group, amorphilinyl group, a substituted morphilinyl group, a pyranyl group, asubstituted pyranyl group, a tetrahydropyranyl group, a substitutedtetrahydropyranyl group, a quinolinyl group, a substituted quinolinylgroup, a pyrrolyl group, a substituted pyrrolyl group, a pyrrolidinylgroup, a substituted pyrrolidinyl group, a piperidinyl group, or asubstituted piperidinyl group, and L³ represents the linking group andis a bond or a C₁ to C₁₀ organyl group.
 63. A catalyst systemcomprising: a) an N²-phosphinyl amidine metal salt complex,characterized by having the formula:

wherein: R¹ is a C₁ to C₃₀ organyl group, R² is a C₁ to C₃₀ organylgroup consisting essentially of inert functional groups R³ is hydrogen,a C₁ to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, R⁴ and R⁵ are each independentlya C₁ to C₃₀ organyl group consisting essentially of inert functionalgroups, MX_(p) represents the metal salt where M is a transition metal,X is a monoanion, and p ranges from 2 to 6, Q is a neutral ligand, and aranges from 0 to 6; and b) a metal alkyl.
 64. The catalyst system ofclaim 63, wherein R¹ comprises a metal complexing group and a linkinggroup linking the metal complexing group to the N¹ nitrogen atom of anN²-phosphinyl amidine group of the N²-phosphinyl amidine compoundcharacterized by having the formula

wherein Q¹ represents the metal complexing group and is a dialkyl aminylgroup, a dicycloalkyl aminyl group, a di(substituted cycloalkyl) aminylgroup, an N-(alkyl)-N-(cycloalkyl) aminyl group, anN-(alkyl)-N-(substituted cycloalkyl) aminyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) aminyl group, a diaryl aminylgroup, a di(substituted aryl) aminyl group, an N-aryl-N-(substitutedaryl) aminyl group, an N-alkyl-N-aryl aminyl group, anN-alkyl-N-(substituted aryl) aminyl group, a dialkyl phosphinyl group, adicycloalkyl phosphinyl group, a di(substituted cycloalkyl) phosphinylgroup), an N-(alkyl)-N-(cycloalkyl) phosphinyl group, anN-(alkyl)-N-(substituted cycloalkyl) phosphinyl group, anN-(cycloalkyl)-N-(substituted cycloalkyl) phosphinyl group, a diarylphosphinyl group, a di(substituted aryl) phosphinyl group, aP-aryl-P-(substituted aryl) phosphinyl group, a P-alkyl-P-arylphosphinyl group, a P-alkyl-P-(substituted aryl) phosphinyl group, analkyl etheryl group, an aryl etheryl group, a substituted aryl etherylgroup, an alkyl sulfidyl group, an aryl sulfidyl group, a substitutedaryl sulfidyl group, a furanyl group, a substituted furanyl group, athienyl group, a substituted thienyl group, a tetrahydrofuranyl group, asubstituted tetrahydrofuranyl group, a thiophanyl group, a substitutedthiophanyl group, a pyridinyl group, a substituted pyridinyl group, amorphilinyl group, a substituted morphilinyl group, a pyranyl group, asubstituted pyranyl group, a tetrahydropyranyl group, a substitutedtetrahydropyranyl group, a quinolinyl group, a substituted quinolinylgroup, a pyrrolyl group, a substituted pyrrolyl group, a pyrrolidinylgroup, a substituted pyrrolidinyl group, a piperidinyl group, or asubstituted piperidinyl group, and L³ represents the linking group andis a bond or a C₁ to C₁₀ organyl group.
 65. A method of preparing acatalyst system according to claim 63, comprising forming a catalystsystem mixture comprising: a) the N²-phosphinyl amidine metal saltcomplex, characterized by having the formula:

wherein: R¹ is a C₁ to C₃₀ organyl group, R² is a C₁ to C₃₀ organylgroup consisting essentially of inert functional groups R³ is hydrogen,a C₁ to C₃₀ organyl group, or a C₁ to C₃₀ organyl group consistingessentially of inert functional groups, R⁴ and R⁵ are each independentlya C₁ to C₃₀ organyl group consisting essentially of inert functionalgroups, MX_(p) represents the metal salt where M is a transition metal,X is a monoanion, and p ranges from 2 to 6, Q is a neutral ligand, and aranges from 0 to 6; and b) the metal alkyl.
 66. An olefinoligomerization process comprising: a) contacting an olefin and thecatalyst system according to claim 63, wherein the metal alkyl is analuminoxane; and b) forming an olefin oligomer product.
 67. An olefinoligomerization process comprising: a) forming a catalyst system mixtureaccording to claim 65, wherein the metal alkyl is an aluminoxane; b)contacting the catalyst system mixture with an olefin; and c) forming anolefin oligomer product.